High-molecular copolymer containing metal coordination compound and organic electroluminescence element using the same

ABSTRACT

It is an object of the present invention to provide a copolymer containing a metal coordination compound that has blue phosphorescence emission with excellent color purity and, furthermore, to provide a copolymer containing a metal coordination compound that has luminescence of various colors from blue to red and a long operating life. The present invention relates to a metal coordination compound-containing copolymer that contains a metal coordination compound monomer unit represented by any one of Formulae (1) to (12): 
                                                             
and at least one type of monomer unit selected from the group consisting of a substituted or unsubstituted quinoline monomer unit, a substituted or unsubstituted arylene and/or heteroarylene monomer unit, a substituted or unsubstituted branched monomer unit, and a substituted or unsubstituted conjugated monomer unit.

TECHNICAL FIELD

The present invention relates to a novel metal coordinationcompound-containing copolymer and an organic electroluminescent (EL)device employing same.

BACKGROUND ART

In recent years, electroluminescent devices have been attractingattention as, for example, large-area solid-state light sources toreplace incandescent lamps and gas-filled lamps. They have also beenattracting attention as self-luminous displays, and are the mostpromising alternative to liquid crystal displays in the flat paneldisplay (FPD) field. In particular, an organic electroluminescent (EL)device, in which the device material is formed from an organic material,is being commercialized as a low power consumption full-color FPD. Aboveall, polymer-based organic EL devices will be indispensable for futurelarge-screen organic EL displays since the organic material of thepolymer-based organic EL devices is formed from a polymer material forwhich film formation by printing, ink-jet, etc. is simple compared withlow molecular weight-based organic EL devices, which require filmformation in a vacuum system.

Conventionally, polymer-based organic EL devices employ either aconjugated polymer such as poly(p-phenylene-vinylene) (see e.g.International Publication WO90/13148) or a non-conjugated polymer (seee.g. I. Sokolik, et al., J. Appl. Phys. 1993. 74, 3584) as the polymermaterial. However, their luminescence lifetime when used in a device isshort, which gives rise to problems when constructing a full-colordisplay.

With the object of solving these problems, polymer-based organic ELdevices employing various types of polyfluorene-based andpoly(p-phenylene)-based conjugated polymers have been proposed in recentyears, but they are not satisfactory in terms of stability.

As one means for solving this problem, a device utilizingphosphorescence from an excited triplet has been investigated. Ifphosphorescence from an excited triplet can be utilized, it can beexpected that in principle the luminescence quantum yield would be atleast three times that obtained when fluorescence from an excitedsinglet is utilized. Furthermore, while taking into considerationutilization of an exciton resulting from intersystem crossing from thesinglet, which has high energy, to the triplet, it can be expected thatin principle the luminescence quantum yield would be four times greater,that is, it would be 100%.

Examples of research that has been carried out so far include M. A.Baldo et al., Appl. Phys. Left. 1999, 75, 4. In this publication, thematerials below are used. The materials are abbreviated as follows.

Alq₃: an aluminum-quinolinol complex (tris(8-quinolinolato)aluminum)

α-NPD: N,N′-Di-naphthalen-1-yl-N,N′-diphenyl-biphenyl-4,4′-diamine

CBP: 4,4′-N,N′-dicarbazole-biphenyl

BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline

Ir(ppy)₃: iridium-phenylpyridine complex (tris(2-phenylpyridine)iridium)

Examples in which luminescence from a triplet is utilized includeJapanese Patent Application Laid-open Nos. 11-329739, 11-256148, and8-319482.

DISCLOSURE OF INVENTION

While taking into consideration the above-mentioned conventionalproblems, it is an object of the present invention to provide acopolymer containing a metal coordination compound that has blue to redphosphorescence emission with excellent color purity and, furthermore,to provide a copolymer containing a metal coordination compound that hasluminescence of various colors from blue to red and a long operatinglife.

Furthermore, it is another object of the present invention to provide apolymer composition that has blue to red phosphorescence emission withexcellent color purity and, furthermore, to provide a polymercomposition that has luminescence of various colors from blue to red anda long operating life.

Moreover, it is yet another object of the present invention to providean organic electroluminescent device that has light emission of variouscolors from blue to red and excellent luminescence characteristics,reliability, etc.

As a result of an intensive investigation by the present inventors, ithas been found that a copolymer containing a metal coordination compoundhaving as ligands various substituents introduced thereinto is anexcellent material that has blue to red luminescence and a longoperating life, and the present invention has thus been accomplished.

That is, in accordance with the present invention, there is provided ametal coordination compound-containing copolymer comprising a metalcoordination compound monomer unit represented by any one of Formulae(1) to (12):

(in the formulae, M is Ir, Rh, Ru, Os, Pd, or Pt, and n is 1 or 2; ringA is a cyclic compound containing a nitrogen atom bonded to M; X₁ to X₇and R are independently substituents selected from the group consistingof —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, and —NR⁹R¹⁰ (here, R¹ toR¹⁰ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, aC1 to C22 straight-chain, cyclic, or branched alkyl group or acorresponding halogen-substituted alkyl group in which a part or all ofthe hydrogen atoms are substituted by a halogen atom, a C6 to C30 arylgroup, a C2 to C30 heteroaryl group, or a C7 to C30 aralkyl group, or acorresponding halogen-substituted aryl group, halogen-substitutedheteroaryl group, or halogen-substituted aralkyl group, in which a partor all of the hydrogen atoms are substituted by a halogen atom, and R¹to R¹⁰ may be identical to or different from each other), X₁ to X₇ maybe identical to or different from each other, and ring A may have asubstituent that is the same as the groups defined by X₁ to X₇; ring Cis a compound that is bonded to M and that bonds to a linking group; andring C may have a substituent that is the same as the groups defined byX₁ to X₇); and at least one type of monomer unit selected from the groupconsisting of a substituted or unsubstituted quinoline monomer unit, asubstituted or unsubstituted arylene and/or heteroarylene monomer unit,a substituted or unsubstituted branched monomer unit, and a substitutedor unsubstituted conjugated monomer unit.

Furthermore, preferably, there is provided a metal coordinationcompound-containing copolymer, wherein the copolymer comprises a metalcoordination compound monomer unit represented by any one of theFormulae (1) to (12), a substituted or unsubstituted quinoline monomerunit represented by Formulae (13-1):

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene; and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O— (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra′C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and a substituted or unsubstituted arylene and/orheteroarylene monomer unit, the monomer units each being bonded via alinking group represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

Moreover, preferably, there is provided a metal coordinationcompound-containing copolymer, wherein the copolymer comprises a metalcoordination compound monomer unit represented by any one of theFormulae (1) to (12), a substituted or unsubstituted quinoline monomerunit represented by Formulae (13-1):

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene; and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O— (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and a substituted or unsubstituted branched monomer unit, themonomer units each being bonded via a linking group represented byFormula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

Furthermore, preferably, there is provided a metal coordinationcompound-containing copolymer, wherein the copolymer comprises a metalcoordination compound monomer unit represented by any one of theFormulae (1) to (12), and a substituted or unsubstituted conjugatedmonomer unit represented by Formula (13-2):

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R₁ and R₂ mayindependently be a hydrogen atom; n, m, and l are independently 0 or 1,and n, m, and l are not simultaneously 0), the monomer units each beingbonded via a linking group represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

Moreover, preferably, there is provided a metal coordinationcompound-containing copolymer, wherein the copolymer comprises a metalcoordination compound monomer unit represented by any one of theFormulae (1) to (12), a substituted or unsubstituted conjugated monomerunit represented by Formula (13-2):

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R1 and R2 mayindependently be a hydrogen atom; n, m, and l are independently 0 or 1,and n, m, and l are not simultaneously 0), and a substituted orunsubstituted branched monomer unit, the monomer units each being bondedvia a linking group represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

Furthermore, preferably, there is provided the metal coordinationcompound-containing copolymer wherein the substituted or unsubstitutedbranched monomer unit is a branched monomer unit selected from the groupconsisting of Formulae (15):

(in the formulae, a plurality of Y are substituents selected from thegroup consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸(here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branchedalkyl group, or a C2 to C30 aryl or heteroaryl group), may be identicalto or different from each other, and are bonded to a substitutableposition of a benzene ring having a branched skeleton, and p is aninteger of 0 to 4).

Moreover, there is provided a polymer composition comprising a mixtureof the metal coordination compound-containing copolymer and a conjugatedor non-conjugated polymer.

Furthermore, there is provided an organic electroluminescent devicefabricated using the metal coordination compound-containing copolymer orthe polymer composition.

The disclosures of the present invention relate to subject matterdescribed in Japanese Patent Application Nos. 2003-173799, 2003-173874,2003-173933, and 2003-173986 filed on Jun. 18, 2003, and the contents ofthe disclosures therein are incorporated herein by reference.

BEST MODE FOR CARRYING OUT THE INVENTION

With regard to organic EL, in order to obtain blue to redphosphorescence emission, it is necessary to change the energy level ofthe lowest excited state. It is surmised that, since the lifetime of anexcited triplet state is generally longer than that of an excitedsinglet, and a molecule remains in the high energy state for a longperiod of time, a reaction with a surrounding material, a change in thestructure of the molecule itself, a reaction between excitonsthemselves, etc. occurs, and the conventional phosphorescence emissiondevice has a short operating life.

Under such circumstances, the present inventors have carried out variousinvestigations, and as a result it has been found that a copolymercontaining a metal coordination compound monomer unit represented byFormulae (1) to (12) below can serve as a phosphorescent light-emittingmaterial that has a blue to red phosphorescence emission and a longoperating life.

Formulae (1) to (12):

(in the formulae, M is Ir, Rh, Ru, Os, Pd, or Pt, and n is 1 or 2; ringA is a cyclic compound containing a nitrogen atom bonded to M; X₁ to X₇and R are independently substituents selected from the group consistingof —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, and —NR⁹R¹⁰ (here, R¹ toR¹⁰ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, aC1 to C22 straight-chain, cyclic, or branched alkyl group or acorresponding halogen-substituted alkyl group in which a part or all ofthe hydrogen atoms are substituted by a halogen atom, a C6 to C30 arylgroup, a C2 to C30 heteroaryl group, or a C7 to C30 aralkyl group, or acorresponding halogen-substituted aryl group, halogen-substitutedheteroaryl group, or halogen-substituted aralkyl group, in which a partor all of the hydrogen atoms are substituted by a halogen atom, and R¹to R¹⁰ may be identical to or different from each other), X₁ to X₇ maybe identical to or different from each other, and ring A may have asubstituent that is the same as the groups defined by X₁ to X₇; ring Cis a compound that is bonded to M and that bonds to a linking group; andring C may have a substituent that is the same as the groups defined byX₁ to X₇). Here, R¹ to R¹⁰ in X₁ to X₇ and R of the metal coordinationcompound monomer units may have a substituent, and examples of thesubstituent include a halogen atom, a cyano group, an aldehyde group, anamino group, an alkyl group, an alkoxy group, an alkylthio group, acarboxyl group, a sulfonic acid group, and a nitro group. Thesesubstituents may be further substituted with a halogen atom, a methylgroup, etc.

Examples of the substituents X₁ to X₇ and R are listed below, but thepresent invention is not limited thereto.

Examples of —R¹ include a hydrogen atom, a halogen atom such as afluorine atom, a chlorine atom, a bromine atom, or an iodine atom, acyano group, a nitro group, a methyl group, an ethyl group, a propylgroup, an isopropyl group, a cyclopropyl group, a butyl group, anisobutyl group, a tert-butyl group, a cyclobutyl group, a pentyl group,an isopentyl group, a neopentyl group, a cyclopentyl group, a hexylgroup, a cyclohexyl group, a heptyl group, a cycloheptyl group, an octylgroup, a nonyl group, a decyl group, a phenyl group, a tolyl group, axylyl group, a mesityl group, a cumenyl group, a benzyl group, aphenethyl group, a methylbenzyl group, a diphenylmethyl group, a styrylgroup, a cinnamyl group, a biphenyl residue, a terphenyl residue, anaphthyl group, an anthryl group, a fluorenyl group, a furan residue, athiophene residue, a pyrrole residue, an oxazole residue, a thiazoleresidue, an imidazole residue, a pyridine residue, a pyrimidine residue,a pyrazine residue, a triazine residue, a quinoline residue, aquinoxaline residue, and derivatives thereof substituted with a halogensuch as a fluorine atom, a chlorine atom, a bromine atom, or an iodineatom.

Examples of —OR² include a hydroxyl group, a methoxy group, an ethoxygroup, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxygroup, a tert-octyloxy group, a phenoxy group, a 4-tert-butylphenoxygroup, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 9-anthryloxygroup.

Examples of —SR³ include a mercapto group, a methylthio group, anethylthio group, a tert-butylthio group, a hexylthio group, an octylthiogroup, a phenylthio group, a 2-methylphenylthio group, and a4-tert-butylphenylthio group.

Examples of —OCOR⁴ include a formyloxy group, an acetoxy group, and anbenzoyloxy group.

Examples of —COOR⁵ include a carboxyl group, a methoxycarbonyl group, anethoxycarbonyl group, a tert-butoxycarbonyl group, a phenoxycarbonylgroup, and a naphthyloxycarbonyl group.

Examples of —SiR⁶R⁷R⁸ include a silyl group, a trimethylsilyl group, atriethylsilyl group, and a triphenylsilyl group.

Examples of —NR⁹R¹⁰ include an amino group, an N-methylamino group, anN-ethylamino group, an N,N-dimethylamino group, an N,N-diethylaminogroup, an N,N-diisopropylamino group, an N,N-dibutylamino group, anN-benzylamino group, an N,N-dibenzylamino group, an N-phenylamino group,and an N,N-diphenylamino group.

The metal coordination compounds used in the present invention havephosphorescent light emission, and it is thought that the lowest excitedstate is either a triplet MLCT (Metal-to-Ligand charge transfer) excitedstate or a π-π* excited state. Phosphorescent light emission occurs whenthere is a transition from such a state to the ground state.

The phosphorescence quantum yield of light-emitting materials of thepresent invention is as high as 0.1 to 0.9, and the phosphorescencelifetime is 1 to 60 μs. Short phosphorescence lifetime is a requirementfor achieving a high luminescence efficiency when used as an organic ELdevice. That is, if the phosphorescence lifetime is long, the proportionof molecules in an excited triplet state is high, and the luminescenceefficiency decreases due to T-T annihilation when the current density ishigh. Since the metal coordination compound-containing copolymer of thepresent invention has high phosphorescence emission efficiency and ashort luminescence lifetime, it is suitable as a light-emitting materialfor an organic EL device.

Furthermore, with regard to the metal coordination compound-containingcopolymer, the energy level of its lowest excited state can be changedby variously changing the substituents on the metal coordinationcompound monomer units represented by Formulae (1) to (12), and it issuitable as an organic EL light-emitting material having blue to redlight emission.

In the metal coordination compound monomer units represented by Formulae(1) to (12) above, M is preferably iridium.

Moreover, ring A is preferably any one of the cyclic compounds havingthe structures shown below, is more preferably pyridine, quinoline,benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole,pyrazole, oxazole, thiazole, triazole, benzopyrazole, triazine, orisoquinoline, which may have a substituent that is the same as thegroups defined by X₁ to X₇ (hereinafter collectively referred to assubstituents Xn), and is yet more preferably pyridine, quinoline, orisoquinoline.

(Here, Z₁ to Z₆ are independently substituents selected from the groupconsisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, and —NR⁹R¹⁰(here, R¹ to R¹⁰ are a hydrogen atom, a halogen atom, a cyano group, anitro group, a C1 to C22 straight-chain, cyclic, or branched alkyl groupor a corresponding halogen-substituted alkyl group in which a part orall of the hydrogen atoms are substituted by a halogen atom, a C6 to C30aryl group, a C2 to C30 heteroaryl group, or a C7 to C30 aralkyl group,or a corresponding halogen-substituted aryl group, halogen-substitutedheteroaryl group, or halogen-substituted aralkyl group, in which a partor all of the hydrogen atoms are substituted by a halogen atom, and R¹to R¹⁰ may be identical to or different from each other), and Z₁ to Z₆may be identical to or different from each other.) Here, R¹ to R¹⁰ mayhave a substituent, and examples of the substituent include a halogenatom, a cyano group, an aldehyde group, an amino group, an alkyl group,an alkoxy group, an alkylthio group, a carboxyl group, a sulfonic acidgroup, and a nitro group. These substituents may be further substitutedwith a halogen atom, a methyl group, etc.

Furthermore, ring C, which is another ligand bonded to Metal M, is abidentate ligand that may have a substituent that is the same as thegroup defined by X₁ to X₇, and is bonded to Metal M to form a ring. RingC is preferably any of the compounds having the structures shown below.

W is a divalent to hexavalent group that reacts with another monomerunit to form a copolymer, and is preferably divalent or trivalent.Examples of W include divalent to hexavalent groups that are the samesubstituents as X₁ to X₈ below and can be bonded to a linking grouprepresented by Formula (14).

X₁ to X₈ are substituents selected from the group consisting of —R¹,—OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, and —NR⁹R¹⁰ (here, R¹ to R¹⁰ area hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1 toC22 straight-chain, cyclic, or branched alkyl group or a correspondinghalogen-substituted alkyl group in which a part or all of the hydrogenatoms are substituted by a halogen atom, a C6 to C30 aryl group, a C2 toC30 heteroaryl group, or a C7 to C30 aralkyl group, or a correspondinghalogen-substituted aryl group, halogen-substituted heteroaryl group, orhalogen-substituted aralkyl group, in which a part or all of thehydrogen atoms are substituted by a halogen atom, and R¹ to R¹⁰ may beidentical to or different from each other), and X₁ to X₈ may beidentical to or different from each other). Here, R¹ to R¹⁰ may have asubstituent, and examples of the substituent include a halogen atom, acyano group, an aldehyde group, an amino group, an alkyl group, analkoxy group, an alkylthio group, a carboxyl group, a sulfonic acidgroup, and a nitro group. These substituents may be further substitutedwith a halogen atom, a methyl group, etc.

(Detailed Description of Method for Synthesizing Metal CoordinationCompound Monomer Unit)

The method for synthesizing a monomer unit used in the present inventionis explained in detail below with reference to specific examples.

The metal coordination compound monomer unit used for the metalcoordination compound-containing copolymer of the present invention canbe produced by various synthetic methods known to a person skilled inthe art. For example, a method described in S. Lamansky et al., J. Am.Chem. Soc. 2001, 123 can be employed. One example of a synthetic routefor a metal coordination compound monomer unit represented by Formulae(1) to (12) above (a case in which ring A is a substituted pyridine) isillustrated using an iridium coordination compound monomer unit as anexample. The explanation below concerns (2) in Table 1 below, and otherexample compounds can also be synthesized by substantially the samemethod.

(Synthesis of Ligand L₁)

(Synthesis of Iridium Complex Monomer Unit)

Here, L₂ is a ring C compound that is bonded to Metal M (iridium in theabove-mentioned case) and is bonded to a linking group.

Preferred embodiments of the metal coordination compound monomer unit inthe present invention are shown below.

For example, with regard to the metal coordination compound monomerunits represented by Formulae (1) to (6) above, when a bluelight-emitting material is to be obtained, at least one of thesubstituents Xn and the substituents of ring A defined as being the sameas Xn is, from the viewpoint of it being effective in reducing thewavelength of light emission, preferably a halogen atom, a cyano group,or a halogen-substituted alkyl group, more preferably a fluorine atom, achlorine atom, a cyano group, or a trifluoromethyl group, yet morepreferably a fluorine atom or a trifluoromethyl group, and mostpreferably a fluorine atom. When at least one of the substituents Xn andthe substituents of ring A defined as being the same as Xn is any one ofthe above-mentioned substituents, the other Xn are often hydrogen atoms,but may be another substituent. For example, X₇ is preferably an alkylgroup or a halogen-substituted alkyl group.

Furthermore, for example, in the metal coordination compound monomerunits represented by Formulae (1) to (6) above, when a green to redlight-emitting material is to be obtained, at least one of thesubstituents Xn and the substituents of ring A defined as being the sameas Xn is preferably —R, —OR, or —SR from the viewpoint of it being easyto control the emission color so that it is green to red. When at leastone of the substituents Xn and the substituents of ring A defined asbeing the same as Xn is any one of the above-mentioned substituents, theother Xn are often hydrogen atoms, but may be another substituent. Forexample, X₇ is preferably an alkyl group, an aryl group, or a heteroarylgroup.

Moreover, for example, in the metal coordination compound monomer unitsrepresented by Formulae (7) to (12) above, when a blue light-emittingmaterial is to be obtained, it is preferable to use a compound in whichB is >C═O or >SO₂. When a green to red emission wavelength is to beobtained, B is preferably >O, >S, or >CR₂. Furthermore, in Formulae (7)to (12) above, at least one of the substituents Xn and the substituentsof ring A defined as being the same as Xn is, from the viewpoint of ablue emission color being obtained, preferably a halogen atom, a cyanogroup, or a halogen-substituted alkyl group, more preferably a fluorineatom, a chlorine atom, a cyano group, or a trifluoromethyl group, yetmore preferably a fluorine atom or a trifluoromethyl group, and mostpreferably a fluorine atom. It is also preferably —R, —OR, or —SR fromthe viewpoint of it being easy to control the emission color so that itis blue to red. When at least one of the substituents Xn and thesubstituents of ring A defined as being the same as Xn is any one of theabove-mentioned substituents, the other Xn are often hydrogen atoms, butmay be another substituent.

Among the metal coordination compounds represented by Formulae (1) to(6) above, the metal coordination compounds represented by Formulae (1),or (4) are preferable from the viewpoint of ease of synthesis. Among themetal coordination compounds represented by Formulae (7) to (12) above,the metal coordination compounds represented by Formulae (8) or (11) arepreferable from the viewpoint of ease of synthesis.

As specific examples of the metal coordination compound monomer unit,example compounds are shown below, but they should not be construed asbeing limited thereto.

(Examples of Metal Coordination Compounds)

TABLE 1 No M n Carbazole unit X₇ Ring A X₁ X₂ X₃ X₄ Ring C (L₂) (1) Ir 2

CH₃

H H H H

(2) Ir 2

CH₃

H H H H

(3) Ir 2

CH₃

H H H H

(4) Ir 2

C₂H₅

H CF₃ H H

(5) Ir 2

C₂H₅

H CF₃ H H

(6) Ir 2

C₂H₅

H CF₃ H H

(7) Ir 2

C₂H₅

H H CF₃ H

(8) Ir 2

C₂H₅

H H CF₃ H

(9) Ir 2

C₂H₅

H H CF₃ H

(10) Ir 2

C₂H₅

H H NO₂ H

(11) Ir 2

C₂H₅

H H NO₂ H

(12) Ir 2

C₂H₅

H H NO₂ H

(13) Ir 2

C₂H₅

H H F H

(14) Ir 2

C₂H₅

H H F H

(15) Ir 2

C₂H₅

H H F H

(16) Ir 2

C₂H₅

H H CN H

(17) Ir 2

C₂H₅

H H CN H

(18) Ir 2

C₂H₅

H H CN H

(19) Ir 2

CH₂CF₃

H H H H

(20) Ir 2

CH₂CF₃

H H H H

(21) Ir 2

CH₂CF₃

H H H H

(22) Ir 2

CH₂CF₃

H CF₃ H H

(23) Ir 2

CH₂CF₃

H CF₃ H H

(24) Ir 2

CH₂CF₃

H CF₃ H H

(25) Ir 2

CH₂CF₃

H H CF₃ H

(26) Ir 2

CH₂CF₃

H H CF₃ H

(27) Ir 2

CH₂CF₃

H H CF₃ H

(28) Ir 2

CH₂CF₃

H H NO₂ H

(29) Ir 2

CH₂CF₃

H H NO₂ H

(30) Ir 2

CH₂CF₃

H H NO₂ H

(31) Ir 2

CH₂CF₃

H H F H

(32) Ir 2

CH₂CF₃

H H F H

(33) Ir 2

CH₂CF₃

H H F H

(34) Ir 2

CH₂CF₃

H H CN H

(35) Ir 2

CH₂CF₃

H H CN H

(36) Ir 2

CH₂CF₃

H H CN H

(37) Ir 2

CH₃

H H H H

(38) Ir 2

CH₃

H H H H

(39) Ir 2

CH₃

H H H H

(40) Ir 2

CH₃

H CF₃ H H

(41) Ir 2

CH₃

H CF₃ H H

(42) Ir 2

CH₃

H CF₃ H H

(43) Ir 2

CH₃

H H CF₃ H

(44) Ir 2

CH₃

H H CF₃ H

(45) Ir 2

CH₃

H H CF₃ H

(46) Ir 2

CH₃

H H NO₂ H

(47) Ir 2

CH₃

H H NO₂ H

(48) Ir 2

CH₃

H H F H

(49) Ir 2

CH₃

H H F H

(50) Ir 2

CH₃

H H F H

(51) Ir 2

CH₃

H H F H

(52) Ir 2

CH₃

H H CN H

(53) Ir 2

CH₃

H H CN H

(54) Ir 2

CH₃

H H CN H

(55) Ir 2

CH₂CF₃

H H H H

(56) Ir 2

CH₂CF₃

H H H H

(57) Ir 2

CH₂CF₃

H H H H

(58) Ir 2

CH₂CF₃

H CF₃ H H

(59) Ir 2

CH₂CF₃

H CF₃ H H

(60) Ir 2

CH₂CF₃

H CF₃ H H

(61) Ir 2

CH₂CF₃

H H CF₃ H

(62) Ir 2

CH₂CF₃

H H CF₃ H

(63) Ir 2

CH₂CF₃

H H CF₃ H

(64) Ir 2

CH₂CF₃

H H NO₂ H

(65) Ir 2

CH₂CF₃

H H NO₂ H

(66) Ir 2

CH₂CF₃

H H NO₂ H

(67) Ir 2

CH₂CF₃

H H F H

(68) Ir 2

CH₂CF₃

H H F H

(69) Ir 2

CH₂CF₃

H H F H

(70) Ir 2

CH₂CF₃

H H CN H

(71) Ir 2

CH₂CF₃

H H CN H

(72) Ir 2

CH₂CF₃

H H CN H

(73) Ir 2

t-C₄H₉

H H H H

(74) Ir 2

t-C₄H₉

H H H H

(75) Ir 2

t-C₄H₉

H H H H

(76) Ir 2

t-C₄H₉

H CF₃ H H

(77) Ir 2

t-C₄H₉

H CF₃ H H

(78) Ir 2

t-C₄H₉

H CF₃ H H

(79) Ir 2

t-C₄H₉

H H CF₃ H

(80) Ir 2

t-C₄H₉

H H CF₃ H

(81) Ir 2

t-C₄H₉

H H CF₃ H

(82) Ir 2

t-C₄H₉

H H NO₂ H

(83) Ir 2

t-C₄H₉

H H NO₂ H

(84) Ir 2

t-C₄H₉

H H NO₂ H

(85) Ir 2

t-C₄H₉

H H F H

(86) Ir 2

t-C₄H₉

H H F H

(87) Ir 2

t-C₄H₉

H H F H

(88) Ir 2

t-C₄H₉

H H CN H

(89) Ir 2

t-C₄H₉

H H CN H

(90) Ir 2

t-C₄H₉

H H CN H

(91) Rh 2

C₂H₅

H CF₃ H H

(92) Rh 2

C₂H₅

H CF₃ H H

(93) Rh 2

C₂H₅

H CF₃ H H

(94) Ru 2

C₂H₅

H CF₃ H H

(95) Ru 2

C₂H₅

H CF₃ H H

(96) Ru 2

C₂H₅

H CF₃ H H

(97) Os 2

C₂H₅

H CF₃ H H

(98) Os 2

C₂H₅

H CF₃ H H

(99) Os 2

C₂H₅

H CF₃ H H

(100) Pd 1

C₂H₅

H CF₃ H H

(101) Pd 1

C₂H₅

H CF₃ H H

(102) Pt 1

C₂H₅

H CF₃ H H

(103) Pt 1

C₂H₅

H CF₃ H H

(104) Ir 2

C₂H₅

H H H H

(105) Ir 2

C₂H₅

H H H H

(106) Ir 2

C₂H₅

H H H H

(107) Ir 2

C₂H₅

H H CF₃ H

(108) Ir 2

C₂H₅

H H CF₃ H

(109) Ir 2

C₂H₅

H H CF₃ H

(110) Ir 2

C₂H₅

H H H H

(111) Ir 2

C₂H₅

H H H H

(112) Ir 2

C₂H₅

H H H H

(113) Ir 2

C₂H₅

H

— —

(114) Ir 2

CH₂CF₃

H H H H

(116) Ir 2

C₂H₅

H H H H

(117) Ir 2

C₂H₅

H H H H

(118) Ir 2

C₂H₅

H H H H

(119) Ir 2

C₂H₅

H H H H

(120) Ir 2

C₂H₅

H

— —

(121) Ir 2

CH₂CF₃

H H H H

(122) Ir 2

C₂H₅

H H H H

(123) Ir 2

C₂H₅

H H H H

(124) Ir 2

C₂H₅

H H H H

(125) Ir 2

C₂H₅

H H H H

TABLE 2 No M n Carbazole unit X₇ Ring A X₁ X₂ X₃ X₄ Ring C (L₂) (125) Ir2

CH₃

H H H H

(126) Ir 2

CH₃

H H H H

(127) Ir 2

CH₃

H H H H

(128) Ir 2

C₂H₅

H CH₃ H H

(129) Ir 2

C₂H₅

H CH₃ H H

(130) Ir 2

C₂H₅

H CH₃ H H

(131) Ir 2

C₂H₅

H H CH₃ H

(132) Ir 2

C₂H₅

H H CH₃ H

(133) Ir 2

C₂H₅

H H CH₃ H

(134) Ir 2

C₂H₅

H H H OCH₃

(135) Ir 2

C₂H₅

H H H OCH₃

(136) Ir 2

C₂H₅

H H H OCH₃

(137) Ir 2

C₂H₅

H H N(CH₃)₂ H

(138) Ir 2

C₂H₅

H H N(CH₃)₂ H

(139) Ir 2

C₂H₅

H H N(CH₃)₂ H

(140) Ir 2

C₂H₅

H CH₃ H H

(141) Ir 2

C₂H₅

H CH₃ H H

(142) Ir 2

C₂H₅

H CH₃ H H

(143) Ir 2

C₂H₅

H H CH₃ H

(144) Ir 2

C₂H₅

H H CH₃ H

(145) Ir 2

C₂H₅

H H CH₃ H

(146) Ir 2

C₂H₅

H H H OCH₃

(147) Ir 2

C₂H₅

H H H OCH₃

(148) Ir 2

C₂H₅

H H H OCH₃

(149) Ir 2

C₂H₅

H H N(CH₃)₂ H

(150) Ir 2

C₂H₅

H H N(CH₃)₂ H

(151) Ir 2

C₂H₅

H H N(CH₃)₂ H

(152) Ir 2

t-C₄H₉

H CH₃ H H

(153) Ir 2

t-C₄H₉

H CH₃ H H

(154) Ir 2

t-C₄H₉

H CH₃ H H

(155) Ir 2

t-C₄H₉

H H CH₃ H

(156) Ir 2

t-C₄H₉

H H CH₃ H

(157) Ir 2

t-C₄H₉

H H CH₃ H

(158) Ir 2

t-C₄H₉

H H H OCH₃

(159) Ir 2

t-C₄H₉

H H H OCH₃

(160) Ir 2

t-C₄H₉

H H H OCH₃

(161) Ir 2

t-C₄H₉

H H N(CH₃)₂ H

(162) Ir 2

t-C₄H₉

H H N(CH₃)₂ H

(163) Ir 2

t-C₄H₉

H H N(CH₃)₂ H

(164) Ir 2

C₂H₅

H H H H

(165) Ir 2

C₂H₅

H H H H

(166) Ir 2

C₂H₅

H H H H

(167) Ir 2

C₂H₅

H CH₃ H H

(168) Ir 2

C₂H₅

H CH₃ H H

(169) Ir 2

C₂H₅

H CH₃ H H

(170) Ir 2

C₂H₅

H H CH₃ H

(171) Ir 2

C₂H₅

H H CH₃ H

(172) Ir 2

C₂H₅

H H CH₃ H

(173) Ir 2

C₂H₅

H H H OCH₃

(174) Ir 2

C₂H₅

H H H OCH₃

(175) Ir 2

C₂H₅

H H H OCH₃

(176) Ir 2

C₂H₅

H H N(CH₃)₂ H

(177) Ir 2

C₂H₅

H H N(CH₃)₂ H

(178) Ir 2

C₂H₅

H H N(CH₃)₂ H

(179) Ir 2

H H H H

(180) Ir 2

H H H H

(181) Ir 2

H H H H

(182) Ir 2

H CH₃ H H

(183) Ir 2

H CH₃ H H

(184) Ir 2

H CH₃ H H

(185) Ir 2

H H CH₃ H

(186) Ir 2

H H CH₃ H

(187) Ir 2

H H CH₃ H

(188) Ir 2

H H H OCH₃

(189) Ir 2

H H H OCH₃

(190) Ir 2

H H H OCH₃

(191) Ir 2

H H N(CH₃)₂ H

(192) Ir 2

H H N(CH₃)₂ H

(193) Ir 2

H H N(CH₃)₂ H

(194) Ir 2

H H H H

(195) Ir 2

H H H H

(196) Ir 2

H H H H

(197) Ir 2

H CH₃ H H

(198) Ir 2

H CH₃ H H

(199) Ir 2

H CH₃ H H

(200) Ir 2

H H CH₃ H

(201) Ir 2

H H CH₃ H

(202) Ir 2

H H CH₃ H

(203) Ir 2

H H H OCH₃

(204) Ir 2

H H H OCH₃

(205) Ir 2

H H H OCH₃

(206) Ir 2

H H N(CH₃)₂ H

(207) Ir 2

H H N(CH₃)₂ H

(208) Ir 2

H H N(CH₃)₂ H

(209) Ir 2

H H H H

(210) Ir 2

H H H H

(211) Ir 2

H H H H

(212) Ir 2

H CH₃ H H

(213) Ir 2

H CH₃ H H

(214) Ir 2

H CH₃ H H

(215) Ir 2

H H CH₃ H

(216) Ir 2

H H CH₃ H

(217) Ir 2

H H CH₃ H

(218) Ir 2

H H H OCH₃

(219) Ir 2

H H H OCH₃

(220) Ir 2

H H H OCH₃

(221) Ir 2

H H N(CH₃)₂ H

(222) Ir 2

H H N(CH₃)₂ H

(223) Ir 2

H H N(CH₃)₂ H

(224) Rh 2

C₂H₅

H H CH₃ H

(225) Rh 2

C₂H₅

H H CH₃ H

(226) Rh 2

C₂H₅

H H CH₃ H

(227) Ru 2

C₂H₅

H H CH₃ H

(228) Ru 2

C₂H₅

H H CH₃ H

(229) Ru 2

C₂H₅

H H CH₃ H

(230) Os 2

C₂H₅

H H CH₃ H

(231) Os 2

C₂H₅

H H CH₃ H

(232) Os 2

C₂H₅

H H CH₃ H

(233) Pd 1

C₂H₅

H H CH₃ H

(234) Pd 1

C₂H₅

H H CH₃ H

(235) Pt 1

C₂H₅

H H CH₃ H

(236) Pt 1

C₂H₅

H H CH₃ H

(237) Ir 2

C₂H₅

H CH₃ H H

(238) Ir 2

C₂H₅

H CH₃ H H

(239) Ir 2

C₂H₅

H CH₃ H H

(240) Ir 2

C₂H₅

H H CH₃ H

(241) Ir 2

C₂H₅

H H CH₃ H

(242) Ir 2

C₂H₅

H H CH₃ H

(243) Ir 2

H H H H

(244) Ir 2

H H H H

(245) Ir 2

H H H H

(246) Ir 2

H

— —

(247) Ir 2

H H H H

(248) Ir 2

H H H H

(249) Ir 2

H H H H

(250) Ir 2

H H H H

(251) Ir 2

H H H H

(252) Ir 2

H

— —

TABLE 3 No M n Condensed ring unit Ring A X₁ X₂ X₃ X₄ Ring C (L₂) (253)Ir 2

H H H H

(254) Ir 2

H H H H

(255) Ir 2

H H H H

(256) Ir 2

H CH₃ H H

(257) Ir 2

H CH₃ H H

(258) Ir 2

H CH₃ H H

(259) Ir 2

H H CH₃ H

(260) Ir 2

H H CH₃ H

(261) Ir 2

H H CH₃ H

(262) Ir 2

H H H OCH₃

(263) Ir 2

H H H OCH₃

(264) Ir 2

H H H OCH₃

(265) Ir 2

H H N(CH₃)₂ H

(266) Ir 2

H H N(CH₃)₂ H

(267) Ir 2

H H N(CH₃)₂ H

(268) Ir 2

H CF₃ H H

(269) Ir 2

H CF₃ H H

(270) Ir 2

H CF₃ H H

(271) Ir 2

H H CF₃ H

(272) Ir 2

H H CF₃ H

(273) Ir 2

H H CF₃ H

(274) Ir 2

H H NO₂ H

(275) Ir 2

H H NO₂ H

(276) Ir 2

H H NO₂ H

(277) Ir 2

H H F H

(278) Ir 2

H H F H

(279) Ir 2

H H F H

(280) Ir 2

H H CN H

(281) Ir 2

H H CN H

(282) Ir 2

H H CN H

(283) Ir 2

H H H H

(284) Ir 2

H H H H

(285) Ir 2

H H H H

(286) Ir 2

H CH₃ H H

(287) Ir 2

H CH₃ H H

(288) Ir 2

H CH₃ H H

(289) Ir 2

H H CH₃ H

(290) Ir 2

H H CH₃ H

(291) Ir 2

H H CH₃ H

(292) Ir 2

H H H OCH₃

(293) Ir 2

H H H OCH₃

(294) Ir 2

H H H OCH₃

(295) Ir 2

H H N(CH₃)₂ H

(296) Ir 2

H H N(CH₃)₂ H

(297) Ir 2

H H N(CH₃)₂ H

(298) Ir 2

H CF₃ H H

(299) Ir 2

H CF₃ H H

(300) Ir 2

H CF₃ H H

(301) Ir 2

H H CF₃ H

(302) Ir 2

H H CF₃ H

(303) Ir 2

H H CF₃ H

(304) Ir 2

H H NO₂ H

(305) Ir 3

H H NO₂ H

(306) Ir 2

H H NO₂ H

(307) Ir 2

H H F H

(308) Ir 2

H H F H

(309) Ir 2

H H F H

(310) Ir 2

H H CN H

(311) Ir 2

H H CN H

(312) Ir 2

H H CN H

(313) Ir 2

H H H H

(314) Ir 2

H H H H

(315) Ir 2

H H H H

(316) Ir 2

H CH₃ H H

(317) Ir 2

H CH₃ H H

(318) Ir 2

H CH₃ H H

(319) Ir 2

H H CH₃ H

(320) Ir 2

H H CH₃ H

(321) Ir 2

H H CH₃ H

(322) Ir 2

H H H OCH₃

(323) Ir 2

H H H OCH₃

(324) Ir 2

H H H OCH₃

(325) Ir 2

H H N(CH₃)₂ H

(326) Ir 2

H H N(CH₃)₂ H

(327) Ir 2

H H N(CH₃)₂ H

(328) Ir 2

H CF₃ H H

(329) Ir 2

H CF₃ H H

(330) Ir 2

H CF₃ H H

(331) Ir 2

H H CF₃ H

(332) Ir 2

H H CF₃ H

(333) Ir 2

H H CF₃ H

(334) Ir 2

H H NO₂ H

(335) Ir 2

H H NO₂ H

(336) Ir 2

H H NO₂ H

(337) Ir 2

H H F H

(338) Ir 2

H H F H

(339) Ir 2

H H F H

(340) Ir 2

H H CN H

(341) Ir 2

H H CN H

(342) Ir 2

H H CN H

(343) Ir 2

H H H H

(344) Ir 2

H H H H

(345) Ir 2

H H H H

(346) Ir 2

H CH₃ H H

(347) Ir 2

H CH₃ H H

(348) Ir 2

H CH₃ H H

(349) Ir 2

H H CH₃ H

(350) Ir 2

H H CH₃ H

(351) Ir 2

H H CH₃ H

(352) Ir 2

H H H H

(353) Ir 2

H H H H

(354) Ir 2

H H H H

(355) Ir 2

H CH₃ H H

(356) Ir 2

H CH₃ H H

(357) Ir 2

H CH₃ H H

(358) Ir 2

H H CH₃ H

(359) Ir 2

H H CH₃ H

(360) Ir 2

H H CH₃ H

(361) Ir 2

H H H OCH₃

(362) Ir 2

H H H OCH₃

(363) Ir 2

H H H OCH₃

(364) Ir 2

H H N(CH₃)₂ H

(365) Ir 2

H H N(CH₃)₂ H

(366) Ir 2

H H N(CH₃)₂ H

(367) Ir 2

H CF₃ H H

(368) Ir 3

H CF₃ H H

(369) Ir 2

H CF₃ H H

(370) Ir 2

H H CF₃ H

(371) Ir 2

H H CF₃ H

(372) Ir 2

H H CF₃ H

(373) Ir 2

H H NO₂ H

(374) Ir 2

H H NO₂ H

(375) Ir 2

H H NO₂ H

(376) Ir 2

H H F H

(377) Ir 2

H H F H

(378) Ir 2

H H F H

(379) Ir 2

H H CN H

(380) Ir 2

H H CN H

(381) Ir 2

H H CN H

(382) Ir 2

H H H H

(383) Ir 2

H H H H

(384) Ir 2

H H H H

(385) Ir 2

H CH₃ H H

(386) Ir 2

H CH₃ H H

(387) Ir 2

H CH₃ H H

(388) Ir 2

H H CH₃ H

(389) Ir 2

H H CH₃ H

(390) Ir 2

H H CH₃ H

(391) Ir 2

H H H OCH₃

(392) Ir 2

H H H OCH₃

(393) Ir 2

H H H OCH₃

(394) Ir 2

H H N(CH₃)₂ H

(395) Ir 2

H H N(CH₃)₂ H

(396) Ir 2

H H N(CH₃)₂ H

(397) Ir 2

H CF₃ H H

(398) Ir 2

H CF₃ H H

(399) Ir 2

H CF₃ H H

(400) Ir 2

H H CF₃ H

(401) Ir 3

H H CF₃ H

(402) Ir 2

H H CF₃ H

(403) Ir 2

H H NO₂ H

(404) Ir 2

H H NO₂ H

(405) Ir 2

H H NO₂ H

(406) Ir 2

H H F H

(407) Ir 2

H H F H

(408) Ir 2

H H F H

(409) Ir 2

H H CN H

(410) Ir 2

H H CN H

(411) Ir 2

H H CN H

(412) Ir 2

H H H H

(413) Ir 2

H H H H

(414) Ir 2

H H H H

(415) Rh 2

H H CH₃ H

(416) Rh 2

H H CH₃ H

(417) Rh 2

H H CH₃ H

(418) Ru 2

H H CH₃ H

(419) Ru 2

H H CH₃ H

(420) Ru 2

H H CH₃ H

(421) Os 2

H H CH₃ H

(422) Os 2

H H CH₃ H

(423) Os 2

H H CH₃ H

(424) Pd 1

H H CH₃ H

(425) Pd 1

H H CH₃ H

(426) Pt 1

H H CH₃ H

(427) Pt 1

H H CH₃ H

(428) Ir 2

H CH₃ H H

(429) Ir 2

H CH₃ H H

(430) Ir 2

H CH₃ H H

(431) Ir 2

H H CH₃ H

(432) Ir 2

H H CH₃ H

(433) Ir 2

H H CH₃ H

(434) Ir 2

H H H H

(435) Ir 3

H H H H

(436) Ir 3

H H H H

(437) Ir 2

H

— —

(438) Ir 2

H H H H

(439) Ir 2

H H H H

(440) Ir 2

H H H H

(441) Ir 2

H H H H

(442) Ir 2

H H H H

(443) Ir 2

H

— —

Furthermore, as specific examples of the metal coordination compoundmonomer unit of the present invention, compounds obtained by replacingring C of the compounds shown in Tables 1 to 3 above with the followingligands can be cited.

The metal coordination compound-containing copolymer of the presentinvention is a copolymer comprising any one of the metal coordinationcompound monomer units represented by Formulae (1) to (12) above, and atleast one type of monomer unit selected from the group consisting of asubstituted or unsubstituted quinoline monomer unit, a substituted orunsubstituted arylene and/or heteroarylene monomer unit, a substitutedor unsubstituted branched monomer unit, and a substituted orunsubstituted conjugated monomer unit.

With regard to the substituted or unsubstituted quinoline monomer unit,the substituted or unsubstituted arylene and/or heteroarylene monomerunit, the substituted or unsubstituted branched monomer unit, and thesubstituted or unsubstituted conjugated monomer unit, monomer units thatare explained in preferred embodiments shown in [1] to [4] below can beused.

In the metal coordination compound-containing copolymer of the presentinvention, as a group linking each monomer unit, linking groupsexplained in [1] below can be used.

The metal coordination compound-containing copolymer of the presentinvention may contain at least each of the above-mentioned monomercomponents, and each of the monomer units may be contained randomly inthe copolymer as in a so-called random copolymer, or it may be acopolymer in which certain monomer units are localized as in a blockcopolymer or a graft copolymer. Each of the monomer units forming theabove-mentioned copolymer may be a single type of monomer or acombination of two or more types of monomers.

Preferred embodiments of the metal coordination compound-containingcopolymer of the present invention are shown below.

[I] A metal coordination compound-containing copolymer comprising

a metal coordination compound monomer unit represented by any one of theFormulae (1) to (12),

a substituted or unsubstituted quinoline monomer unit represented byFormulae (13-1):

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene, and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O— (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and

a substituted or unsubstituted arylene and/or heteroarylene monomerunit.

It is preferable that the group linking the monomer units is a linkinggroup represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

The quinoline monomer unit used in the present invention and representedby Formulae (13-1):

can be used singly or in a combination of two or more types.

Among the quinoline monomer units of Formulae (13-1) of the presentinvention, a plurality of V are represented by —R¹, —OR², —SR³, —OCOR⁴,—COOR⁵, or —SiR⁶R⁷R⁸, and when there is a plurality of substituents V,they may be identical to or different from each other. Each a isindependently an integer of 0 to 3.

Furthermore, R¹ to R⁸ of the substituent V are independently a C1 to C22straight-chain alkyl, cyclic alkyl, or branched alkyl group, or a C2 toC30 aryl or heteroaryl group. Examples of such groups include C1 to C22straight-chain alkyl, cyclic alkyl, or branched alkyl groups such asmethyl, ethyl, propyl, cyclopropyl, butyl, isobutyl, cyclobutyl, pentyl,isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl,cycloheptyl, octyl, nonyl, and decyl, and C2 to C30 aryl or heteroarylgroups such as phenyl, naphthyl, anthracenyl, a biphenyl residue, aterphenyl residue, a furan residue, a thiophene residue, a pyrroleresidue, an oxazole residue, a thiazole residue, an imidazole residue, apyridine residue, a pyrimidine residue, a pyrazine residue, a triazineresidue, a quinoline residue, and a quinoxaline residue.

The substituent V may further have a substituent. Examples of thesubstituent on V include a substituent represented by theabove-mentioned —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, or —SiR⁶R⁷R⁸, and asubstituent represented by —NR⁹R¹⁰ (here, R⁹ and R¹⁰ are independently aC1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 toC20 aryl or heteroaryl group). When there is a plurality ofsubstituents, the plurality of substituents may be identical to ordifferent from each other.

Among the quinoline monomer units of Formulae (13-1) in the presentinvention, with regard to each Va independently, it is preferable, fromthe viewpoint of solubility and heat resistance, for a to be 0, that is,the monomer unit is unsubstituted, or for V to be an alkyl or aryl groupsubstituent represented by —R¹. With regard to the number ofsubstituents, including a case in which a is 0, that is, the monomerunit is unsubstituted, a is preferably 1 or 2 from the viewpoint ofpolymerization reactivity. Furthermore, as the aryl group phenyl ispreferable.

In the quinoline monomer units of Formulae (13-1), each D isindependently a single bond or arylene, preferably arylene, andpreferably, from the viewpoint of polymerization reactivity,ortho-phenylene, meta-phenylene, or para-phenylene.

E is a divalent linking group selected from the group consisting of asingle bond, —O—, —S—, —C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)_(m)—O— (mis an integer of 1 to 3), and -Q-. The above-mentioned W is a divalentgroup selected from the group consisting of —Ra—, —Ar′—, —Ra—Ar′—,—Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—, —Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—,—Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—, —Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—,and —Ar′-Q-Ar′—, Ra is an alkylene group, Ar′ is an arylene group, eachRa′ is independently a group selected from the group consisting ofalkylene, arylene, and a mixed alkylene/arylene group, Het′ is aheteroarylene group, and Q is a divalent group containing a quaternarycarbon. E is preferably a single bond, —O—, —Ar′—, or —Ra′—O—Ra′— and,from the viewpoint of polymerization reactivity, is preferably a phenylresidue, a phenanthrene residue, a fluorene residue, a carbazoleresidue, a biphenyl residue, or a diphenyl ether residue.

Other than these, with regard to alkylene, arylene, heteroarylene, and Qas divalent groups D or E, there can be cited as examples divalentgroups obtained by removing one hydrogen atom from the substituentscited as examples of R¹ to R⁸ in the above-mentioned substituent V.

In Formulae (13-1), the divalent group represented by D or E may have asubstituent. Examples of the substituent possessed by D or E includesubstituents such as the above-mentioned —R¹, —OR², —SR³, —OCOR⁴,—COOR⁵, —SiR⁶R⁷R⁸, or —NR⁹R¹⁰. When there is a plurality ofsubstituents, the plurality of substituents may be identical to ordifferent from each other.

As specific examples of the quinoline monomer units of Formulae (13-1),example compounds are listed below, but they should not be cons trued asbeing limited thereto.

Here, in the above-mentioned quinoline monomer units, examples of thesubstituent R include substituents represented by the above-mentioned—R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, or —NR⁹R¹⁰. R may be ahydrogen atom. The substituents R may be identical to or different fromeach other.

With regard to the substituted or unsubstituted arylene and/orheteroarylene monomer unit used in the present invention, a divalentgroup is preferable; examples thereof include benzene, biphenyl,terphenyl, naphthalene, anthracene, tetracene, fluorene, phenanthrene,pyrene, chrysene, pyridine, pyrazine, isoquinoline, acridine,phenanthroline, furan, pyrrole, thiophene, oxazole, oxadiazole,thiadiazole, triazole, benzoxazole, benzoxadiazole, benzothiadiazole,benzothiophene, diphenyloxadiazole, benzothiadiazole, diphenyldiazole,and diphenylthiadiazole, and they are used as the arylene and/orheteroarylene monomer unit either singly or in a manner in which aplurality thereof are bonded. The arylene and/or heteroarylene monomerunits may be used singly or in a combination of two or more types.

The arylene and/or heteroarylene monomer unit may have a substituent,and examples of the substituent include substituents represented by —R¹,—OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, or —NR⁹R¹⁰. When there is aplurality of substituents, the plurality of substituents may beidentical to or different from each other.

The above-mentioned R¹ to R⁸ are independently a C1 to C22straight-chain, cyclic, or a branched alkyl group or a C2 to C30 aryl orheteroaryl group. Examples of these groups include C1 to C22straight-chain alkyl, cyclic alkyl, or branched alkyl groups such as amethyl group, an ethyl group, a propyl group, a cyclopropyl group, abutyl group, an isobutyl group, a cyclobutyl group, a pentyl group, anisopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group,a cyclohexyl group, a heptyl group, a cycloheptyl group, an octyl group,a nonyl group, and a decyl group, and C2 to C30 aryl or heteroarylgroups such as a phenyl group, a naphthyl group, an anthracenyl group, abiphenyl residue, a terphenyl residue, a furan residue, a thiopheneresidue, a pyrrole residue, an oxazole residue, a thiazole residue, animidazole residue, a pyridine residue, a pyrimidine residue, a pyrazineresidue, a triazine residue, a quinoline residue, and a quinoxalineresidue. The substituent possessed by the arylene and/or heteroarylenemonomer unit may further have a substituent.

It is preferable from the viewpoint of solubility and heat resistancethat the substituents possessed by the arylene and/or heteroarylenemonomer unit of the present invention are independently a hydrogen atom,that is, the monomer unit is unsubstituted, —R¹ in which the monomerunit is substituted with an alkyl group, an aryl group, or a heteroarylgroup, or —OR² in which the monomer unit is substituted with an alkoxygroup, an aryloxy group, or a heteroaryloxy group. From the viewpoint ofpolymerization reactivity the number of substituents, including a casein which the substituent is a hydrogen atom, that is, the monomer unitis unsubstituted, is preferably 1 to 3. Furthermore, the aryl group ispreferably a substituted or unsubstituted phenyl group, a substituted orunsubstituted fluorene group, etc. Moreover, the heteroaryl group ispreferably an oxadiazole group, a phenyloxadiazole group, aphenylthiadiazole group, a benzothiadiazole group, etc.

As representative examples, those represented by the structural formulaebelow can be cited.

Substituents R of these arylene and/or heteroarylene monomer units areindependently substituents selected from the group consisting of —R¹,—OR², —SR³, —OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a hydrogenatom, a C1 to C22 straight-chain, cyclic, or branched alkyl group, or aC2 to C30 aryl or heteroaryl group), which may be identical to ordifferent from each other, and are substituents that are bonded to asubstitutable position of the arylene and/or heteroarylene skeleton.

Among these substituents, it is preferable from the viewpoint ofpolymerization reactivity and heat resistance that each R isindependently a hydrogen atom in which the monomer unit isunsubstituted, —R¹ in which the monomer unit is substituted with analkyl group, an aryl group, or a heteroaryl group, or —OR² in which themonomer unit is substituted with a hydroxyl group, an alkoxy group, anaryloxy group, or a heteroaryloxy group.

In the metal coordination compound-containing copolymer [I] of thepresent invention, it is preferable that the group linking the monomerunits is a linking group represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

In the above-mentioned Formula (14), when b is 0, it means a singlebond. Among these, the linking group is preferably a single bond or —O—,from the viewpoint of ease of synthesis. R in —R—O—R—, —NR—, —CR₂—,—SiR₂—, —SiR₂—O—SiR₂—, or —SiR₂—O—SiR₂—O—SiR₂— is preferably a C1 to C22straight-chain, cyclic, or branched alkyl group from the viewpoint ofimparting solubility, and particularly preferably, from the viewpoint ofpolymerization reactivity, a C1 to C6 straight-chain alkyl group.

The metal coordination compound-containing copolymer [I] of the presentinvention contains at least the above-mentioned three monomer unitcomponents and, if necessary, may contain as a ‘comonomer unit’, thatis, a monomer unit other than the above-mentioned monomer units, amonomer unit having a substituted or unsubstituted triphenylamineskeleton. Examples of such a monomer unit having a triphenylamineskeleton include triphenylamine, N-(4-butylphenyl)-N,N-diphenylamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine, andN,N′-bis(3-methylphenyl)-N,N′-bis(2-naphthyl)-[1,1′-biphenyl]-4,4′-diamine.With regard to groups that can substitute these aromatic rings, therecan be cited as examples C1 to C22 alkyl and alkoxy groups.

The mole fraction of the metal coordination compound monomer unitrelative to the total number of monomer units of the metal coordinationcompound-containing copolymer [I] of the present invention is preferably0.1% to 30%, more preferably 0.5% to 20%, and most preferably 1% to 10%.When the metal coordination compound monomer unit is present at lessthan 0.1%, the luminescence chromaticity tends to deteriorate, and whenit exceeds 30%, the luminance tends to decrease.

The mole fraction of the quinoline monomer unit relative to the totalnumber of monomer units of the metal coordination compound-containingcopolymer [I] of the present invention is preferably 1% to 70%, morepreferably 3% to 65%, and most preferably 5% to 50%. When the quinolinemonomer unit is present at less than 1%, the luminance tends todecrease, and when it exceeds 70%, the luminescence chromaticity tendsto deteriorate.

The mole fraction of the arylene and/or heteroarylene unit relative tothe total number of monomer units of the metal coordinationcompound-containing copolymer [I] of the present invention is preferably1% to 99%, more preferably 3% to 97%, and most preferably 5% to 95%.When the arylene and/or heteroarylene unit is present at less than 1%,the luminance tends to decrease, and when it exceeds 99%, theluminescence chromaticity tends to deteriorate.

The mole fraction of the monomer unit having a substituted orunsubstituted triphenylamine skeleton that can be copolymerized with themetal coordination compound-containing copolymer [I] of the presentinvention is preferably 0% to 30% of the total number of monomer unitsof the polymer.

The metal coordination compound-containing copolymer [I] of the presentinvention can be produced by various synthetic methods known to a personskilled in the art. For example, when there is no group linking each ofthe monomer units, methods reported by T. Yamamoto et al. in Bull. Chem.Soc. Jap., Vol. 51, No. 7, p. 2091 (1978), and by M. Zembayashi et al.in Tet. Lett., Vol. 47, p. 4089 (1977) can be employed, and a methodreported by Suzuki in Synthetic Communications, Vol. 11, No. 7, p. 513(1981) is generally used for production of a copolymer. This reactioninvolves a Pd-catalyzed cross-coupling reaction between an aromaticboronic acid derivative and an aromatic halide (normally called the‘Suzuki reaction’), and enables the metal coordinationcompound-containing copolymer [I] of the present invention to beproduced by a reaction that links the respective aromatic ringstogether.

This reaction requires a soluble Pd compound in the form of a Pd(II)salt or a Pd(0) complex. As the Pd source, 0.01 to 5 mol %, relative tothe aromatic reactants, of Pd(PPh₃)₄, a complex between a tertiaryphosphine ligand and Pd(OAc)₂, or a PdCl₂(dppf) complex is generallypreferable. This reaction also requires a base, and an aqueous alkalicarbonate or bicarbonate is most preferable. The reaction can bepromoted by the use of a phase-transfer catalyst in a nonpolar solvent.As the solvent, N,N-dimethylformamide, toluene, dimethoxyethane,tetrahydrofuran, etc. can be used.

In the case of the polymer [I] of the present invention, specifically,for example, it can be produced by copolymerization of a diboronic acidester of a quinoline derivative represented by the formulae below

(in the formulae, R′ is a lower alkyl group such as methyl, ethyl, orpropyl, or a lower alkylene group such as ethylene or propylene in whichtwo R′ groups are bonded to each other to form a ring, and V, D, E, anda are as described above) with a dibromo metal coordination compoundderivative monomer and a dibromoarylene and/or dibromoheteroarylenemonomer in the presence of a palladium (0) catalyst using awater-soluble base.

When the group linking each of the monomer units is —O—, the metalcoordination compound-containing copolymer of the present invention canbe produced by a reaction, in a polar solvent in the presence of a base,between a difluoroquinoline monomer, a dihydroxy metal coordinationcompound derivative monomer, and a dihydroxyarylene and/ordihyroxyheteroarylene monomer, between a dibromo metal coordinationcompound derivative monomer, a dibromoarylene and/ordibromoheteroarylene monomer, and a dihydroxyquinoline monomer, orbetween a dibromoquinoline monomer, a dibromoarylene and/ordibromoheteroarylene monomer, and a dihydroxy metal coordinationcompound derivative monomer, as disclosed in Japanese Patent ApplicationLaid-open No. 9-136954. This reaction is carried out by a reaction forproducing the metal coordination compound-containing copolymer of thepresent invention in the presence of a base that can deprotonate adihydroxy compound. Examples of such a base include alkali metal oralkaline earth metal carbonates or hydroxides such as potassiumcarbonate, potassium hydroxide, sodium carbonate, and sodium hydroxide.When the acidity of the dihydroxy compound is too low for it to besufficiently deprotonated by sodium hydroxide, a stronger base such as ametal hydride, for example, sodium hydride, butyllithium, or a metalamide, for example, sodium amide, may be used. Water is generated duringa reaction between this base and the dihydroxy compound. This water canbe removed by azeotropic distillation.

The metal coordination compound-containing copolymer [I] of the presentinvention can further be copolymerized with another monomer, andexamples of other dihydroxy monomers include isopropylidenediphenol(bisphenol A), 1,2-di(4-hydroxyphenyl)ethane,di(4-hydroxyphenyl)methane, N,N-bis(4-hydroxyphenyl)-N-phenylamine, andN,N′-bis(4-hydroxyphenyl)-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine.

[II] A metal coordination compound-containing copolymer comprising

a metal coordination compound monomer unit represented by any one of theFormulae (1) to (12),

a substituted or unsubstituted quinoline monomer unit represented byFormulae (13-1):

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene; and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O— (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and

a substituted or unsubstituted branched monomer unit.

It is preferable that the group linking the monomer units is a linkinggroup represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

The quinoline monomer unit represented by Formulae (13-1) used in thepresent invention is the same as the quinoline monomer unit in theabove-mentioned [I].

The substituted or unsubstituted branched monomer unit used in thepresent invention is preferably a unit having a tri- or higher-valentbranched structure, and more preferably a unit having a trivalent ortetravalent branched structure. As the branched monomer unit, branchedstructures represented by Formulae (15):

are preferable, and these branched monomer units may be used singly orin a combination of two or more types.

The substituents Y in Formulae (15) for these branched monomer units aresubstituents selected from the group consisting of —R¹, —OR², —SR³,—OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl orheteroaryl group), may be identical to or different from each other, andare bonded to a substitutable position of a benzene ring having abranched skeleton, and p is an integer of 0 to 4. It is preferable for pto be 0 to 2.

Furthermore, R¹ to R⁸ of the substituent Y are independently a C1 to C22straight-chain alkyl, cyclic alkyl, or branched alkyl group, or a C2 toC30 aryl or heteroaryl group. Examples of such groups include C1 to C22straight-chain alkyl, cyclic alkyl, or branched alkyl groups such asmethyl, ethyl, propyl, cyclopropyl, butyl, isobutyl, cyclobutyl, pentyl,isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl,cycloheptyl, octyl, nonyl, and decyl, and C2 to C30 aryl or heteroarylgroups such as phenyl, naphthyl, anthracenyl, a biphenyl residue, aterphenyl residue, a furan residue, a thiophene residue, a pyrroleresidue, an oxazole residue, a thiazole residue, an imidazole residue, apyridine residue, a pyrimidine residue, a pyrazine residue, a triazineresidue, a quinoline residue, and a quinoxaline residue.

The substituent Y may further have a substituent. Examples of thesubstituent on Y include a substituent represented by theabove-mentioned —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, or —SiR⁶R⁷R⁸, and asubstituent represented by —NR⁹R¹⁰ (here, R⁹ and R¹⁰ are independently aC1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 toC20 aryl or heteroaryl group). When there is a plurality ofsubstituents, the plurality of substituents may be identical to ordifferent from each other.

Among these substituents, with regard to each Yp independently, it ispreferable, from the viewpoint of polymerization reactivity and heatresistance, for p to be 0, that is, the monomer unit is unsubstituted,or for Y to be an alkyl group substituent represented by —R¹. Withregard to the number of substituents, including a case in which p is 0,that is, the monomer unit is unsubstituted, p is preferably 1 from theviewpoint of polymerization reactivity.

In the metal coordination compound-containing copolymer [II] of thepresent invention, a group linking each monomer unit and represented byFormula (14) is the same as the linking group in the above-mentioned[I].

The metal coordination compound-containing copolymer [II] of the presentinvention contains at least the above-mentioned three monomer unitcomponents and, if necessary, may contain as a ‘comonomer unit’, thatis, a monomer unit other than the above-mentioned monomer units, amonomer unit having a substituted or unsubstituted triphenylamineskeleton. As such a monomer unit having a triphenylamine skeleton, thesame ones as the monomer units having a triphenylamine skeleton in theabove-mentioned [I] can be used.

Furthermore, the metal coordination compound-containing copolymer [II]of the present invention contains at least the above-mentioned threemonomer unit components and, if necessary, may contain as a ‘comonomerunit’, that is, a monomer unit other than the above-mentioned monomerunits, a monomer unit having a substituted or unsubstituted aryleneand/or heteroarylene monomer unit. As such a substituted orunsubstituted arylene and/or heteroarylene monomer unit, the same onesas the arylene and/or heteroarylene monomer units in the above-mentioned[I] can be used.

The mole fraction of the metal coordination compound monomer unitrelative to the total number of monomer units of the metal coordinationcompound-containing copolymer [II] of the present invention ispreferably 0.1% to 30%, more preferably 0.5% to 20%, and most preferably1% to 10%. When the metal coordination compound monomer unit is presentat less than 0.1%, the luminescence chromaticity tends to deteriorate,and when it exceeds 30%, the luminance tends to decrease.

The mole fraction of the quinoline monomer unit relative to the totalnumber of monomer units of the metal coordination compound-containingcopolymer [II] of the present invention is preferably 1% to 70%, morepreferably 3% to 65%, and most preferably 5% to 50%. When the quinolinemonomer unit is present at less than 1%, the luminance tends todecrease, and when it exceeds 70%, the luminescence chromaticity tendsto deteriorate.

The mole fraction of the substituted or unsubstituted branched monomerunit relative to the total number of monomer units of the metalcoordination compound-containing copolymer [II] of the present inventionis preferably 0.1% to 30%, more preferably 0.5% to 20%, and mostpreferably 1% to 10%. When the branched monomer unit is present at lessthan 0.1%, the luminescence chromaticity tends to deteriorate, and whenit exceeds 30%, the luminance tends to decrease.

The mole fraction of the monomer unit having a substituted orunsubstituted triphenylamine skeleton or a substituted or unsubstitutedarylene and/or heteroarylene monomer unit that can be copolymerized withthe metal coordination compound-containing copolymer [II] of the presentinvention is preferably 0% to 48% of the total number of monomer unitsof the polymer.

The metal coordination compound-containing copolymer [II] of the presentinvention can be produced by the same synthetic method as that for theabove-mentioned [I].

In the case of the polymer [II] of the present invention, for example,when there is no group linking each of the monomer units, specifically,it can be produced by copolymerization of a diboronic acid ester of aquinoline derivative represented by the formulae below

(in the formulae, R′ is a lower alkyl group such as methyl, ethyl, orpropyl, or a lower alkylene group such as ethylene or propylene in whichtwo R′ groups are bonded to each other to form a ring, and V, D, E, anda are as described above) with a dibromo metal coordination compoundderivative monomer and a tribromo branched derivative in the presence ofa palladium (0) catalyst using a water-soluble base.

When the group linking each of the monomer units is —O—, the metalcoordination compound-containing copolymer of the present invention canbe produced by a reaction, in a polar solvent in the presence of a base,between a difluoroquinoline monomer, a dihydroxy metal coordinationcompound derivative monomer, and a trihydroxy branched derivative,between a dibromo metal coordination compound derivative monomer, atribromo branched derivative, and a dihydroxyquinoline monomer, orbetween a dibromoquinoline monomer, a tribromo branched derivative, anda dihydroxy metal coordination compound derivative monomer, as disclosedin Japanese Patent Application Laid-open No. 9-136954.

The metal coordination compound-containing copolymer [II] of the presentinvention can further be copolymerized with another monomer, and asexamples of other dihydroxy monomers the same ones as the dihydroxymonomers in the above-mentioned [I] can be used.

[III] A metal coordination compound-containing copolymer comprising

a metal coordination compound monomer unit represented by any one ofFormulae (1) to (12), and

a substituted or unsubstituted conjugated monomer unit represented byFormula (13-2):

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R₁ and R₂ mayindependently be a hydrogen atom; n, m, and l are independently 0 or 1,and n, m, and l are not simultaneously 0).

It is preferable that the group linking the monomer units is a linkinggroup represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

The conjugated monomer unit represented by Formula (13-2):

used in the present invention can be used singly or in a combination oftwo or more types.

In the monomer unit of Formula (13-2) of the present invention, Ar₁ andAr₂ are divalent arylene and/or heteroarylene, a plurality of V, and R₁and R₂, are independently substituents selected from the groupconsisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸ (here, R¹to R⁸ are a C1 to C22 straight-chain, cyclic, or branched alkyl group,or a C2 to C30 aryl or heteroaryl group), may be identical to ordifferent from each other, and are bonded to a substitutable position ofan arylene or heteroarylene residue, and a and b are independently aninteger of 0 or greater. R₁ and R₂ may independently be a hydrogen atom,n, m, and l are independently 0 or 1, and n, m, and l are notsimultaneously 0). Ar₁ and Ar₂ may be identical to or different fromeach other, and when there is a plurality of substituents V, thesesubstituents may be identical to or different from each other.

In the Formula (13-2), Ar₁ and Ar₂ are substituted or unsubstitutedarylene and/or heteroarylene. With regard to such substituted orunsubstituted arylene and/or heteroarylene, a divalent group ispreferable; examples thereof include benzene, biphenyl, terphenyl,naphthalene, anthracene, tetracene, fluorene, phenanthrene, pyrene,chrysene, pyridine, pyrazine, isoquinoline, acridine, phenanthroline,furan, pyrrole, thiophene, oxazole, oxadiazole, thiadiazole, triazole,benzoxazole, benzoxadiazole, benzothiadiazole, benzothiophene,diphenyloxadiazole, benzothiadiazole, diphenyldiazole, anddiphenylthiadiazole, and they are used as Ar₁ and Ar₂ either singly orin a manner in which a plurality thereof are bonded.

Furthermore, R¹ to R⁸ of the substituents V, R₁, and R₂ areindependently a C1 to C22 straight-chain alkyl, cyclic alkyl, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group. Examplesof such groups include C1 to C22 straight-chain alkyl, cyclic alkyl, orbranched alkyl groups such as methyl, ethyl, propyl, cyclopropyl, butyl,isobutyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl,cyclohexyl, heptyl, cycloheptyl, octyl, nonyl, and decyl, and C2 to C30aryl or heteroaryl groups such as phenyl, naphthyl, anthracenyl, abiphenyl residue, a terphenyl residue, a furan residue, a thiopheneresidue, a pyrrole residue, an oxazole residue, a thiazole residue, animidazole residue, a pyridine residue, a pyrimidine residue, a pyrazineresidue, a triazine residue, a quinoline residue, and a quinoxalineresidue.

The substituents V, R₁, and R₂ may further have a substituent. Examplesof the substituent on V, R₁, and R₂ include a substituent represented bythe above-mentioned —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, or —SiR⁶R⁷R⁸, and asubstituent represented by —NR⁹R¹⁰ (here, R⁹ and R¹⁰ are independently aC1 to C22 straight-chain, cyclic, or branched alkyl group, or a C2 toC20 aryl or heteroaryl group). When there is a plurality ofsubstituents, the plurality of substituents may be identical to ordifferent from each other.

Among the conjugated monomer units of Formula (13-2) in the presentinvention, it is preferable, from the viewpoint of solubility and heatresistance, for V, R₁, and R₂ to be independently a hydrogen atom, thatis, the monomer unit is unsubstituted, —R¹ in which the monomer unit issubstituted with an alkyl, aryl, or heteroaryl group, or —OR² in whichthe monomer unit is substituted with an alkoxy, aryloxy, orheteroaryloxy group. With regard to the number of substituents,including a case in which a or b is 0, that is, the monomer unit isunsubstituted, a or b is preferably 1 to 3 from the viewpoint ofpolymerization reactivity. Furthermore, the aryl group is preferably asubstituted or unsubstituted phenyl group, a substituted orunsubstituted fluorene group, etc. Moreover, the heteroaryl group ispreferably an oxadiazole group, a phenyloxadiazole group, aphenylthiadiazole group, a benzothiadiazole group, etc.

Representative examples of Ar₁ and Ar₂ include those represented by thestructural formulae below.

Substituents R of these arylene and/or heteroarylene are independentlysubstituents selected from the group consisting of —R¹, —OR², —SR³,—OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a hydrogen atom, a C1to C22 straight-chain, cyclic, or branched alkyl group, or a C2 to C30aryl or heteroaryl group), which may be identical to or different fromeach other, and are substituents that are bonded to a substitutableposition of the arylene and/or heteroarylene skeleton.

Among these substituents, it is preferable from the viewpoint ofpolymerization reactivity and heat resistance that each R isindependently a hydrogen atom, that is, the monomer unit isunsubstituted, —R¹ in which the monomer unit is substituted with analkyl group, an aryl group, or a heteroaryl group, or —OR² in which themonomer unit is substituted with a hydroxyl group, an alkoxy group, anaryloxy group, or a heteroaryloxy group.

In the metal coordination compound-containing copolymer [III] of thepresent invention, a group linking each monomer unit and represented byFormula (14) is the same as the linking group in the above-mentioned[I].

The metal coordination compound-containing copolymer [III] of thepresent invention contains at least the above-mentioned two monomer unitcomponents and, if necessary, may contain as a ‘comonomer unit’, thatis, a monomer unit other than the above-mentioned monomer units, amonomer unit having a substituted or unsubstituted triphenylamineskeleton. As such a monomer unit having a triphenylamine skeleton, thesame ones as the monomer unit having a triphenylamine skeleton in theabove-mentioned [I] can be used.

The mole fraction of the metal coordination compound monomer unitrelative to the total number of monomer units of the metal coordinationcompound-containing copolymer [III] of the present invention ispreferably 0.1% to 30%, more preferably 0.5% to 20%, and most preferably1% to 10%. When the metal coordination compound monomer unit is presentat less than 0.1%, the luminescence chromaticity tends to deteriorate,and when it exceeds 30%, the luminance tends to decrease.

The mole fraction of the conjugated monomer unit relative to the totalnumber of monomer units of the metal coordination compound-containingcopolymer [III] of the present invention is preferably 70% to 99.9%,more preferably 75% to 99.5%, and most preferably 80% to 99%. When theconjugated monomer unit is present at less than 70%, the luminance tendsto decrease, and when it exceeds 99.9%, the luminescence chromaticitytends to deteriorate.

The mole fraction of the monomer unit having a substituted orunsubstituted triphenylamine skeleton that can be copolymerized with themetal coordination compound-containing copolymer [III] of the presentinvention is preferably 0% to 49% of the total number of monomer unitsof the polymer.

The metal coordination compound-containing copolymer [III] of thepresent invention can be produced by the same synthetic method as in theabove-mentioned [I].

In the case of the polymer [III] of the present invention, for example,when there is no group linking each of the monomer units, specifically,it can be produced by copolymerization of a diboronic acid ester of aconjugated monomer derivative and/or a dibromo compound of theconjugated monomer derivative, represented by the formula below

(in the formulae, R is a lower alkyl group such as methyl, ethyl, orpropyl, or a lower alkylene group such as ethylene or propylene in whichtwo R groups are bonded to each other to form a ring, and Ar₁, Ar₂, R₁,R₂, V, a, b, n, m, and l are as described above) with a dibromo metalcoordination compound derivative monomer in the presence of a palladium(0) catalyst using a water-soluble base.

When the group linking each of the monomer units is —O—, the metalcoordination compound-containing copolymer of the present invention canbe produced by a reaction, in a polar solvent in the presence of a base,between a difluoro conjugated monomer and a dihydroxy metal coordinationcompound derivative monomer, between a dibromo metal coordinationcompound derivative monomer and a dihydroxy conjugated monomer, orbetween a dibromo conjugated monomer and a dihydroxy metal coordinationcompound derivative monomer, as disclosed in Japanese Patent ApplicationLaid-open No. 9-136954.

The metal coordination compound-containing copolymer [III] of thepresent invention can further be copolymerized with another monomer, andas examples of other dihydroxy monomers the same ones as the dihydroxymonomers in the above-mentioned [I] can be used.

[IV] A metal coordination compound-containing copolymer comprising

a metal coordination compound monomer unit represented by any one of theFormulae (1) to (12),

a substituted or unsubstituted conjugated monomer unit represented byFormula (13-2):

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R1 and R2 mayindependently be a hydrogen atom; n, m, and l are independently 0 or 1,and n, m, and l are not simultaneously 0), and

a substituted or unsubstituted branched monomer unit.

It is preferable that the group linking the monomer units is a linkinggroup represented by Formula (14):-(G)b-  (14)(in the formula, G is a divalent group selected from the groupconsisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—, —SiR₂—O—SiR₂—, and—SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), and b isan integer of 0 or 1).

The conjugated monomer unit represented by Formulae (13-2) used in thepresent invention is the same as the conjugated monomer unit in theabove-mentioned [III].

Furthermore, with regard to the substituted or unsubstituted branchedmonomer unit used in the present invention, ones that are the same asthe branched monomer unit used in the above-mentioned [II] can be used.

In the metal coordination compound-containing copolymer [IV] of thepresent invention, a group linking each monomer unit and represented byFormula (14) is the same as the linking group in the above-mentioned[I].

The metal coordination compound-containing copolymer [IV] of the presentinvention contains at least the above-mentioned two monomer unitcomponents and, if necessary, may contain as a ‘comonomer unit’, thatis, a monomer unit other than the above-mentioned monomer units, amonomer unit having a substituted or unsubstituted triphenylamineskeleton. As such a monomer unit having a triphenylamine skeleton, thesame ones as the monomer unit having a triphenylamine skeleton in theabove-mentioned [I] can be used.

The mole fraction of the metal coordination compound monomer unitrelative to the total number of monomer units of the metal coordinationcompound-containing copolymer [IV] of the present invention ispreferably 0.1% to 30%, more preferably 0.5% to 20%, and most preferably1% to 10%. When the metal coordination compound monomer unit is presentat less than 0.1%, the luminescence chromaticity tends to deteriorate,and when it exceeds 30%, the luminance tends to decrease.

The mole fraction of the conjugated monomer unit relative to the totalnumber of monomer units of the metal coordination compound-containingcopolymer [IV] of the present invention is preferably 50% to 99.9%, morepreferably 60% to 99.5%, and most preferably 75% to 99%. When theconjugated monomer unit is present at less than 50%, the luminance tendsto decrease, and when it exceeds 99.9%, the luminescence chromaticitytends to deteriorate.

The mole fraction of the substituted or unsubstituted branched monomerunit relative to the total number of monomer units of the metalcoordination compound-containing copolymer [IV] of the present inventionis preferably 0.1% to 30%, more preferably 0.5% to 20%, and mostpreferably 1% to 10%. When the substituted or unsubstituted branchedmonomer unit is present at less than 0.1%, the luminescence chromaticitytends to deteriorate, and when it exceeds 30%, the luminance tends todecrease.

The mole fraction of a substituted or unsubstituted triphenylamineskeleton that can be copolymerized with the metal coordinationcompound-containing copolymer [IV] of the present invention ispreferably 0% to 48% of the total number of monomer units of thepolymer.

The metal coordination compound-containing copolymer [IV] of the presentinvention can be produced by the same synthetic method as in theabove-mentioned [I].

In the case of the polymer [IV] of the present invention, for example,when there is no group linking each of the monomer units, specifically,it can be produced by copolymerization of a diboronic acid ester of aconjugated monomer derivative and/or a dibromo compound of theconjugated monomer derivative, represented by the formulae below

(in the formulae, R is a lower alkyl group such as methyl, ethyl, orpropyl, or a lower alkylene group such as ethylene or propylene in whichtwo R groups are bonded to each other to form a ring, and Ar₁, Ar₂, R₁,R₂, V, a, b, n, m, and l are as described above) with a dibromo metalcoordination compound derivative monomer and a tribromo branchedderivative in the presence of a palladium (0) catalyst using awater-soluble base.

When the group linking each of the monomer units is —O—, the metalcoordination compound-containing copolymer of the present invention canbe produced by a reaction, in a polar solvent in the presence of a base,between a difluoro conjugated monomer, a dihydroxy metal coordinationcompound derivative monomer, and a trihydroxy branched derivative,between a dibromo metal coordination compound derivative monomer, atribromo branched derivative, and a dihydroxy conjugated monomer, orbetween a dibromo conjugated monomer, a tribromo branched derivative,and a dihydroxy metal coordination compound derivative monomer, asdisclosed in Japanese Patent Application Laid-open No. 9-136954.

The metal coordination compound-containing copolymer [IV] of the presentinvention can further be copolymerized with another monomer, and asexamples of other dihydroxy monomers the same ones as the dihydroxymonomers in the above-mentioned [I] can be used.

The molecular weight of the metal coordination compound-containingcopolymer of the present invention is preferably 10,000 to 1,000,000,and more preferably 30,000 to 800,000. When it is less than 10,000, thefilm-forming properties tend to deteriorate, and when it exceeds1,000,000, the solubility tends to decrease.

The metal coordination compound-containing copolymer of the presentinvention can be used as a material of an active layer of anelectroluminescent device. The active layer referred to here means alayer that is able to emit light when an electric field is applied(light-emitting layer), or a layer that improves the charge injection orthe charge transporting (charge injection layer or charge transportinglayer). Here, the charge means a negative or a positive charge.

The thickness of the active layer can be set as appropriate while takinginto consideration the luminescence efficiency, etc., and is preferably10 to 300 nm, and more preferably 20 to 200 nm. When it is less than 10nm, pinholes, etc. tend to occur as thin film defects, and when itexceeds 300 nm, the properties tend to deteriorate.

The copolymer of the present invention may be used as a mixture withanother material. Furthermore, the electroluminescent device employingthe copolymer of the present invention may further have a layercontaining a material other than the above-mentioned copolymer layeredwith the active layer containing the copolymer of the present invention.As a material that may be used as a mixture with the copolymer of thepresent invention, a known material such as a positive hole injectionand/or positive hole transporting material, an electron injection and/orelectron transporting material, a light-emitting material, or a binderpolymer can be used. The material mixed may be a high molecular weightmaterial or a low molecular weight material.

Examples of the positive hole injection and/or positive holetransporting material that can be used include materials such as anarylamine derivative, a triphenylmethane derivative, a stilbene-basedcompound, a hydrazone-based compound, a carbazole-based compound, a highmolecular weight arylamine, a polyaniline, and a polythiophene, andmaterials formed by polymerizing the above materials. Examples of theelectron injection and/or electron transporting material that can beused include materials such as an oxadiazole derivative, a benzoxazolederivative, a benzoquinone derivative, a quinoline derivative, aquinoxaline derivative, a thiadiazole derivative, a benzodiazolederivative, a triazole derivative, and a metal chelate complex compound,and materials formed by polymerizing the above materials. Examples ofthe light-emitting material that can be used include an arylaminederivative, an oxadiazole derivative, a perylene derivative, aquinacridone derivative, a pyrazoline derivative, an anthracenederivative, a rubrene derivative, a stilbene derivative, a coumarinderivative, a naphthalene derivative, a metal chelate complex, and ametal complex containing Ir, Pt, etc. as the central metal, materialsformed by polymerizing the above materials, and polymer materials suchas a polyfluorene derivative, a polyphenylenevinylene derivative, apolyphenylene derivative, and a polythiophene derivative. As the binderpolymer that can be used, one that does not greatly degrade theproperties can be used. Examples of the binder polymer includepolystyrene, polycarbonate, polyarylether, polyacrylate,polymethacrylate, and polysiloxane.

In particular, the metal coordination compound-containing copolymer ofthe present invention can be used as a polymer composition in which itis mixed with a conjugated or non-conjugated polymer. Examples of theconjugated or nonconjugated polymer that can be used in the polymercomposition include a polyphenylene derivative, a polyfluorenederivative, a polyphenylene vinylene derivative, a polythiophenederivative, a polyquinoline derivative, a polytriphenylamine derivative,a polyvinylcarbazole derivative, a polyaniline derivative, a polyimidederivative, a polyamideimide derivative, a polycarbonate derivative, apolyacrylic derivative, and a polystyrene derivative, which may besubstituted or unsubstituted. Further examples of these conjugated ornon-conjugated polymers include copolymers thereof with, as necessary,another arylene and/or heteroarylene monomer unit such as benzene,biphenyl, terphenyl, naphthalene, anthracene, tetracene, fluorene,phenanthrene, pyrene, chrysene, pyridine, pyrazine, quinoline,isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene,oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole,benzothiadiazole, or benzothiophene, which may be substituted orunsubstituted, and a monomer unit having a substituted or unsubstitutedtriphenylamine skeleton such as triphenylamine,N-(4-butylphenyl)-N-diphenylamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine, orN,N′-bis(3-methylphenyl)-N,N′-bis(2-naphthyl)-[1,1′-biphenyl]-4,4′-diamine.

In order to use the copolymer or the polymer composition of the presentinvention as a material of the active layer of the electroluminescentdevice, a substrate can be layered with a solution thereof or a filmthereof using a method known to a person skilled in the art, such as,for example, ink jet, casting, spraying, immersion, printing, or spincoating. Examples of the printing method include relief printing,intaglio printing, offset printing, lithographic printing, reverserelief offset printing, screen printing, and gravure printing. Such alayering method can be usually carried out at a temperature in the rangeof −20° C. to +300° C., preferably 10° C. to 100° C., and particularlypreferably 15° C. to 50° C. The layered polymer solution can usually bedried at room temperature or by heating on a hot plate.

As the solvent used for a copolymer-containing solution, chloroform,methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene,mesitylene, anisole, acetone, methyl ethyl ketone, ethyl acetate, butylacetate, ethyl cellosolve acetate, etc. can be used.

The metal coordination compound-containing copolymer is preferablycontained at 0.1 to 5 wt % relative to the total weight of thecopolymer-containing solution, and more preferably 0.2 to 3 wt %. Whenit is less than 0.1 wt %, pinholes, etc. tend to occur as thin filmdefects, and when it exceeds 5 wt %, unevenness in the film thicknesstends to occur. A standard structure for the electroluminescent deviceof the present invention comprising the polymer of the present inventionis described in U.S. Pat. No. 4,539,507 and U.S. Pat. No. 5,151,629. Apolymer-containing electroluminescent device is described in, forexample, International Publication WO90/13148 and EP Pat. Laid-open No.0443861.

These electroluminescent devices usually include an electroluminescentlayer (light-emitting layer) between cathode and anode electrodes, atleast one of which is transparent. Furthermore, at least one electroninjection layer and/or electron transporting layer is inserted betweenthe electroluminescent layer (light-emitting layer) and the cathode and,moreover, at least one positive hole injection layer and/or positivehole transporting layer is inserted between the electroluminescent layer(light-emitting layer) and the anode. As a material for the cathode, forexample, a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Mg/Ag,or LiF is preferable. As the anode, a metal (e.g. Au) or anothermaterial having metallic conductivity such as, for example, an oxide(e.g. ITO: indium oxide/tin oxide) on a transparent substrate (e.g. aglass or a transparent polymer) can be used.

Examples of an electron injection and/or electron transporting layerinclude layers containing materials such as an oxadiazole derivative, abenzoxazole derivative, a benzoquinone derivative, a quinolinederivative, a quinoxaline derivative, a thiadiazole derivative, abenzodiazole derivative, a triazole derivative, or a metal chelatecomplex compound.

Examples of a positive hole injection and/or positive hole transportinglayer include layers containing materials such as copper phthalocyanine,a triphenylamine derivative, a triphenylmethane derivative, astilbene-based compound, a hydrazone-based compound, a carbazole-basedcompound, a high molecular weight arylamine, a polyaniline, or apolythiophene.

The metal coordination compound-containing copolymer of the presentinvention is suitable as, for example, a material for an organic ELdevice. In particular, it exhibits good luminescence color purity, andstability and, furthermore, good film-forming properties due to ease offilm formation, etc. The organic EL device of the present inventionemploying same therefore exhibits good luminescence color purity, andstability, and it is excellent in terms of productivity.

EXAMPLES

The present invention is explained below with reference to examples, butis not limited thereto. It is also possible, other than the examplesshown below, to obtain electroluminescent devices having excellent colorpurity, reliability and luminescence characteristics in cases where theabove-mentioned various monomer units are used.

Example 1 Synthesis of Metal Coordination Compound (1) in Table 1

A Grignard reagent was prepared by gradually adding a THF solution of3-bromo-9-methylcarbazole (30 mmol) to a mixture of magnesium (1.9 g, 80mmol) and THF under a flow of argon while stirring well. The Grignardreagent thus obtained was gradually added dropwise over 2 hours to a THFsolution of trimethyl borate (300 mmol) at −78° C. while stirring well,and the mixture was then stirred at room temperature for 2 days. Thereaction mixture was poured into 5% dilute sulfuric acid containingcrushed ice and stirred. The aqueous solution thus obtained wasextracted with toluene, and the extract was concentrated to give acolorless solid. The solid thus obtained was recrystallized fromtoluene/acetone (1/2) to give a boronic acid carbazole derivative ascolorless crystals (40%). The boronic acid carbazole derivative (12mmol) thus obtained and 1,2-ethanediol (30 mmol) were refluxed intoluene for 10 hours, and then recrystallized from toluene/acetone (1/4)to give a boronic acid ester carbazole derivative as colorless crystals.

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of2-bromopyridine (10 mmol), the boronic acid ester carbazole derivative(10 mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously. Thereaction mixture was cooled to room temperature and then poured into alarge amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give3-(2′-pyridyl)-9-methylcarbazole as a solid.

A 200 ml three-necked flask was charged with iridium (III) chloride (1.7mmol), 3-(2′-pyridyl)-9-methylcarbazole (7.58 mmol), 50 ml ofethoxyethanol, and 20 ml of water, and the mixture was stirred under aflow of nitrogen at room temperature for 30 minutes and then refluxedfor 24 hours while stirring. The reaction mixture was cooled to roomtemperature, and a precipitate was collected by filtration, washed withwater, and then washed with ethanol and acetone in sequence. Theprecipitate was dried under vacuum at room temperature to givedi-μ-chloro-tetrakis[3-(2′-pyridyl)-9-methylcarbazole-N^(1′),C²]diiridium(III) as a pale yellow powder.

A 200 ml three-necked flask was charged with 70 ml of ethoxyethanol,di-p-chloro-tetrakis[3-(2′-pyridyl)-9-methylcarbazole-N^(1′),C²]diiridium(III) (0.7 mmol), the acetylacetone derivative represented by thestructural formula below (2.10 mmol), and sodium carbonate (9.43 mmol),and the mixture was stirred under a flow of nitrogen at room temperatureand then refluxed for 15 hours while stirring.

The reaction mixture was cooled with ice, and a precipitate wascollected by filtration and washed with water. This precipitate waspurified by silica gel column chromatography (eluent:chloroform/methanol: 30/1) to givebis[3-(2′-pyridyl)-9-methylcarbazole-N^(1′),C²](dibromobenzylacetylacetonato)iridium (III) as a pale yellow powder.

Example 2 Synthesis of Metal Coordination Compound (125) in Table 2

A Grignard reagent was prepared by gradually adding a THF solution of2-hydroxy-6-bromo-9-methylcarbazole (30 mmol) to a mixture of magnesium(1.9 g, 80 mmol) and THF under a flow of argon while stirring well. TheGrignard reagent thus obtained was gradually added dropwise over 2 hoursto a THF solution of trimethyl borate (300 mmol) at −78° C. whilestirring well, and the mixture was then stirred at room temperature for2 days. The reaction mixture was poured into 5% dilute sulfuric acidcontaining crushed ice and stirred. The aqueous solution thus obtainedwas extracted with toluene, and the extract was concentrated to give acolorless solid. The solid thus obtained was recrystallized fromtoluene/acetone (1/2) to give a boronic acid carbazole derivative ascolorless crystals (40%). The boronic acid carbazole derivative (12mmol) thus obtained and 1,2-ethanediol (30 mmol) were refluxed intoluene for 10 hours, and then recrystallized from toluene/acetone (1/4)to give a boronic acid ester carbazole derivative as colorless crystals.

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of2-bromopyridine (10 mmol), the boronic acid ester carbazole derivative(10 mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously. Thereaction mixture was cooled to room temperature and then poured into alarge amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give2-hydroxy-6-(2′-pyridyl)-9-methylcarbazole as a solid.

A 200 ml three-necked flask was charged with iridium (III) chloride (1.7mmol), 2-hydroxy-6-(2′-pyridyl)-9-methylcarbazole (7.58 mmol), 50 ml ofethoxyethanol, and 20 ml of water, and the mixture was stirred under aflow of nitrogen at room temperature for 30 minutes and then refluxedfor 24 hours while stirring. The reaction mixture was cooled to roomtemperature, and a precipitate was collected by filtration, washed withwater, and then washed with ethanol and acetone in sequence. Theprecipitate was dried under vacuum at room temperature to givedi-μ-chloro-tetrakis[2-hydroxy-6-(2′-pyridyl)-9-methylcarbazole-N^(1′);C⁷]diiridium (III) as a pale yellow powder.

A 200 ml three-necked flask was charged with 70 ml of ethoxyethanol,di-μ-chloro-tetrakis[2-hydroxy-6-(2′-pyridyl)-9-methylcarbazole-N^(1′),C⁷]diiridium(III) (0.7 mmol), the acetylacetone derivative represented by thestructural formula below (2.10 mmol), and sodium carbonate (9.43 mmol),and the mixture was stirred under a flow of nitrogen at room temperatureand then refluxed for 15 hours while stirring.

The reaction mixture was cooled with ice, and a precipitate wascollected by filtration and washed with water. This precipitate waspurified by silica gel column chromatography (eluent:chloroform/methanol: 30/1) to givebis[2-hydroxy-6-(2′-pyridyl)-9-methylcarbazole-N^(1′),C⁷](dibromobenzylacetylacetonato)iridium(III) as a pale yellow powder.

Example 3 Synthesis of Metal Coordination Compound (253) in Table 3

A Grignard reagent was prepared by gradually adding a THF solution of2-bromo-9-fluorenone (30 mmol) to a mixture of magnesium (1.9 g, 80mmol) and THF under a flow of argon while stirring well. The Grignardreagent thus obtained was gradually added dropwise over 2 hours to a THFsolution of trimethyl borate (300 mmol) at −78° C. while stirring well,and the mixture was then stirred at room temperature for 2 days. Thereaction mixture was poured into 5% dilute sulfuric acid containingcrushed ice and stirred. The aqueous solution thus obtained wasextracted with toluene, and the extract was concentrated to give acolorless solid. The solid thus obtained was recrystallized fromtoluene/acetone (1/2) to give a boronic acid fluorenone derivative ascolorless crystals (40%). The boronic acid fluorenone derivative (12mmol) thus obtained and 1,2-ethanediol (30 mmol) were refluxed intoluene for 10 hours, and then recrystallized from toluene/acetone (1/4)to give a boronic acid ester fluorenone derivative as colorlesscrystals.

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of2-bromopyridine (10 mmol), the boronic acid ester fluorenone derivative(10 mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously. Thereaction mixture was cooled to room temperature and then poured into alarge amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give2-(2′-pyridyl)-9-fluorenone as a solid.

A 200 ml three-necked flask was charged with iridium (III) chloride (1.7mmol), 2-(2′-pyridyl)-9-fluorenone (7.58 mmol), 50 ml of ethoxyethanol,and 20 ml of water, and the mixture was stirred under a flow of nitrogenat room temperature for 30 minutes and then refluxed for 24 hours whilestirring. The reaction mixture was cooled to room temperature, and aprecipitate was collected by filtration, washed with water, and thenwashed with ethanol and acetone in sequence. The precipitate was driedunder vacuum at room temperature to givedi-μ-chloro-tetrakis[2-(2′-pyridyl)-9-fluorenone-N^(1′),C³]diiridium(III) as a pale yellow powder.

A 200 ml three-necked flask was charged with 70 ml of ethoxyethanol,di-μ-chloro-tetrakis[2-(2′-pyridyl)-9-fluorenone-N^(1′),C³]diiridium(III) (0.7 mmol), the acetylacetone derivative represented by thestructural formula below (2.10 mmol), and sodium carbonate (9.43 mmol),and the mixture was stirred under a flow of nitrogen at room temperatureand then refluxed for 15 hours while stirring.

The reaction mixture was cooled with ice, and a precipitate wascollected by filtration and washed with water. This precipitate waspurified by silica gel column chromatography (eluent:chloroform/methanol: 30/1) to givebis[2-(2′-pyridyl)-9-fluorenone-N^(1′),C³](dibromobenzylacetylacetonato)iridium(III) as a pale yellow powder.

Example I-4 Synthesis of Diboronic Acid Ester Quinoline Derivative(I-Q-1)

A Grignard reagent was prepared by gradually adding a THF solution of6,6′-bis[2-(4-bromophenyl)-3,4-diphenylquinoline] (30 mmol) to a mixtureof magnesium (1.9 g, 80 mmol) and THF under a flow of argon whilestirring well. The Grignard reagent thus obtained was gradually addeddropwise over 2 hours to a THF solution of trimethyl borate (300 mmol)at −78° C. while stirring well, and the mixture was then stirred at roomtemperature for 2 days. The reaction mixture was poured into 5% dilutesulfuric acid containing crushed ice and stirred. The aqueous solutionthus obtained was extracted with toluene, and the extract wasconcentrated to give a colorless solid. The solid thus obtained wasrecrystallized from toluene/acetone (1/2) to give a diboronic acidquinoline derivative as colorless crystals (40%). The diboronic acidquinoline derivative (12 mmol) thus obtained and 1,2-ethanediol (30mmol) were refluxed in toluene for 10 hours, and then recrystallizedfrom toluene/acetone (1/4) to give a diboronic acid ester quinolinederivative as colorless crystals (83%).

Example I-5 Synthesis of Metal Coordination Compound-ContainingCopolymer (I-P-1)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (1) synthesized in Example 1 (1 mmol), thedibromodiphenyloxadiazole (9 mmol) and the dicyclohexyloxydibromobenzene(5 mmol) represented by the structural formulae below, the diboronicacid ester quinoline derivative (I-Q-1) synthesized in Example I-4 (5mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(I-P-1).

The compound thus obtained was identified by NMR spectroscopy, IRspectroscopy, etc. The same applies to the compounds shown below.

Example I-6 Synthesis of Metal Coordination Compound-ContainingCopolymer (I-P-2)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (125) synthesized in Example 2 (1 mmol), thedibromodiphenyloxadiazole (9 mmol) and the dicyclohexyloxydibromobenzene(5 mmol) represented by the structural formulae below, the diboronicacid ester quinoline (I-Q-1) derivative synthesized in Example I-4 (5mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(I-P-2).

Example I-7 Synthesis of Metal Coordination Compound-ContainingCopolymer (I-P-3)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (253) synthesized in Example 3 (1 mmol), thedibromodiphenyloxadiazole (9 mmol) and the dicyclohexyloxydibromobenzene(5 mmol) represented by the structural formulae below, the diboronicacid ester quinoline (I-Q-1) derivative synthesized in Example I-4 (5mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(I-P-3).

Example I-8 Fabrication of Organic EL Device (I-1)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (I-P-1) obtained in Example I-5 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order Ca(film thickness 20 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=450 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

Example I-9 Fabrication of Organic EL Device (I-2)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (I-P-2) obtained in Example I-6 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order LiF(film thickness 0.5 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the LiF/Al was the negativeelectrode, at about 5 V emission of orange light (λ=590 nm) wasobserved. No change in the color of this orange light emission wasobserved after 500 hours at 25° C.

Example I-10 Fabrication of Organic EL Device (I-3)

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example I-8 except that the metal coordinationcompound-containing copolymer (I-P-3) was used instead of the metalcoordination compound-containing copolymer (I-P-1). With regard to thecharacteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=450 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

Comparative Example 1

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example I-8 except that a polyquinoline represented bythe structural formula below was used instead of the metal coordinationcompound-containing copolymer (I-P-1). The ITO/light-emitting polymerlayer/Ca/Al device thus obtained was connected to a power supply, avoltage was applied so that the ITO was the positive electrode and theCa/Al was the negative electrode, and at about 10 V emission of bluelight (λ=430 nm) was observed, but the color of the light emissionchanged from blue to pale blue over time.

Comparative Example 2

An ITO/light-emitting polymer layer/LiF/Al device was fabricated in thesame manner as in Example I-8 except that a(dioctylfluorene/benzothiazole) copolymer represented by the structuralformula below was used instead of the metal coordinationcompound-containing copolymer (I-P-1). The ITO/light-emitting polymerlayer/LiF/Al device thus obtained was connected to a power supply, avoltage was applied so that the ITO was the positive electrode and theLiF/Al was the negative electrode, and at about 8 V emission of yellowlight (λ=548 nm) was observed, but the color of the light emissionchanged from yellow to yellowish white over time.

Comparative Example 3

A 40 nm film thickness of α-NPD as a hole-transporting layer was formedon a glass substrate with a 2 mm wide ITO (indium tin oxide) patterningby a vacuum vapor deposition method involving resistive heating in avacuum chamber at 10⁻⁵ Pa. On top of this a ratio by weight of 5% of themetal coordination compound Ir(ppy)₃ represented by the structuralformula below was vapor co-deposited with CBP.

Furthermore, the above-mentioned Alq₃ was vapor deposited thereon as anelectron-transporting layer at 30 nm. On top of this, 0.5 to 2 nm of LiFand 100 to 150 nm of Al were vapor deposited as a negative electrodelayer. With regard to the characteristics of the organic EL device atroom temperature, current/voltage characteristics were measured using a4140B picoammeter manufactured by Hewlett-Packard and the luminance wasmeasured using an SR-3 manufactured by Topcon Corporation. The devicethus obtained was connected to a power supply, a voltage was applied sothat the ITO was the positive electrode and the LiF/Al was the negativeelectrode, and at about 6 V emission of green light (λ=516 nm) wasobserved. The luminance half-life measured when driven at a constantcurrent (50 mA/cm²) was 100 hours.

Example II-4 Synthesis of Diboronic Acid Ester Quinoline Derivative(II-Q-1)

A Grignard reagent was prepared by gradually adding a THF solution of6,6′-bis[2-(4-bromophenyl)-3,4-diphenylquinoline] (30 mmol) to a mixtureof magnesium (1.9 g, 80 mmol) and THF under a flow of argon whilestirring well. The Grignard reagent thus obtained was gradually addeddropwise over 2 hours to a THF solution of trimethyl borate (300 mmol)at −78° C. while stirring well, and the mixture was then stirred at roomtemperature for 2 days. The reaction mixture was poured into 5% dilutesulfuric acid containing crushed ice and stirred. The aqueous solutionthus obtained was extracted with toluene, and the extract wasconcentrated to give a colorless solid. The solid thus obtained wasrecrystallized from toluene/acetone (1/2) to give a diboronic acidquinoline derivative as colorless crystals (40%). The diboronic acidquinoline derivative (12 mmol) thus obtained and 1,2-ethanediol (30mmol) were refluxed in toluene for 10 hours, and then recrystallizedfrom toluene/acetone (1/4) to give a diboronic acid ester quinolinederivative as colorless crystals (83%).

Example II-5 Synthesis of Metal Coordination Compound-ContainingCopolymer (II-P-1)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (1) synthesized in Example 1 (1 mmol), thedibromodiphenyloxadiazole (8 mmol) and the dicyclohexyloxydibromobenzene(5 mmol) represented by the structural formulae below, the diboronicacid ester quinoline derivative (II-Q-1) synthesized in Example II-4 (5mmol), a tribromo branched monomer (1 mmol), and Pd(0)(PPh₃)₄ (0.2 mmol)under a flow of argon, and the mixture was refluxed for 48 hours whilestirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(II-P-1).

Example II-6 Synthesis of Metal Coordination Compound-ContainingCopolymer (II-P-2)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (125) synthesized in Example 2 (1 mmol), thedibromodiphenyloxadiazole (8.5 mmol) and thedicyclohexyloxydibromobenzene (5 mmol) represented by the structuralformulae below, the diboronic acid ester quinoline derivative (II-Q-1)synthesized in Example II-4 (5 mmol), a tribromo branched monomer (0.5mmol), and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and themixture was refluxed for 48 hours while stirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(II-P-2).

Example II-7 Synthesis of Metal Coordination Compound-ContainingCopolymer (II-P-3)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (253) synthesized in Example 3 (1 mmol), thedibromodiphenyloxadiazole (8 mmol) and the dicyclohexyloxydibromobenzene(5 mmol) represented by the structural formulae below, the diboronicacid ester quinoline derivative (II-Q-1) synthesized in Example II-4 (5mmol), a tribromo branched monomer (1 mmol), and Pd(0)(PPh₃)₄ (0.2 mmol)under a flow of argon, and the mixture was refluxed for 48 hours whilestirring vigorously.

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(II-P-3).

Example II-8 Fabrication of Organic EL Device (II-1)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (II-P-1) obtained in Example II-5 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order Ca(film thickness 20 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4.5 V emission of blue light (λ=440 nm) wasobserved. No change in the color of this blue light emission wasobserved after 500 hours at 25° C.

Example II-9 Fabrication of Organic EL Device (II-2)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (II-P-2) obtained in Example II-6 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order LiF(film thickness 0.5 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the LiF/Al was the negativeelectrode, at about 5.5 V emission of orange light (λ=570 nm) wasobserved. No change in the color of this orange light emission wasobserved after 500 hours at 25° C.

Example II-10 Fabrication of Organic EL Device (II-3)

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example II-8 except that the metal coordinationcompound-containing copolymer (II-P-3) was used instead of the metalcoordination compound-containing copolymer (II-P-1). With regard to thecharacteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4.5 V emission of blue light (λ=447 nm) wasobserved. No change in the color of this blue light emission wasobserved after 500 hours at 25° C.

Example III-4 Synthesis of Dicyclohexyloxybenzene Diboronic Acid Ester(III-PP-1)

A Grignard reagent was prepared by gradually adding a THF solution of2,5-dibromo-1,4-dihexyloxybenzene (30 mmol) to a mixture of magnesium(1.9 g, 80 mmol) and THF under a flow of argon while stirring well. TheGrignard reagent thus obtained was gradually added dropwise over 2 hoursto a THF solution of trimethyl borate (300 mmol) at −78° C. whilestirring well, and the mixture was then stirred at room temperature for2 days. The reaction mixture was poured into 5% dilute sulfuric acidcontaining crushed ice and stirred. The aqueous solution thus obtainedwas extracted with toluene, and the extract was concentrated to give acolorless solid. The solid thus obtained was recrystallized fromtoluene/acetone (1/2) to give dicyclohexyloxybenzene diboronic acid ascolorless crystals (50%). The dicyclohexyloxybenzene diboronic acid (12mmol) thus obtained and 1,2-ethanediol (30 mmol) were refluxed intoluene for 10 hours, and then recrystallized from toluene/acetone (1/4)to give a dicyclohexyloxybenzene diboronic acid ester as colorlesscrystals (80%).

Example III-5 Synthesis of Metal Coordination Compound-ContainingCopolymer (III-P-1)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (1) synthesized in Example 1 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (9 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example III-4(10 mmol), represented by the structural formula below, and Pd(0)(PPh₃)₄(0.2 mmol) under a flow of argon, and the mixture was refluxed for 48hours while stirring vigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(III-P-1).

Example III-6 Synthesis of Metal Coordination Compound-ContainingCopolymer (III-P-2)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (125) synthesized in Example 2 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (4 mmol),2-(2,5-dibromophenyl)-5-phenyl[1,3,4]oxadiazole (4 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example III-4(10 mmol), represented by the structural formulae below, andPd(0)(PPh₃)₄ (0.2 mmol) under a flow of argon, and the mixture wasrefluxed for 48 hours while stirring vigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

2-(2,5-Dibromo-phenyl)-5-phenyl-[1,3,4]oxadiazole,

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(III-P-2).

Example III-7 Synthesis of Metal Coordination Compound-ContainingCopolymer (III-P-3)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (253) synthesized in Example 3 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (9 mmol),9,9-dioctylfluorene-2,7-diboronic acid ester (5 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example III-4(5 mmol), represented by the structural formulae below, and Pd(0)(PPh₃)₄(0.2 mmol) under a flow of argon, and the mixture was refluxed for 48hours while stirring vigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

9,9-Dioctylfluorene-2,7-bis(pinacol boronate),

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(III-P-3).

Example III-8 Fabrication of Organic EL Device (III-1)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (III-P-1) obtained in Example III-5 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order Ca(film thickness 20 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=455 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

Example III-9 Fabrication of Organic EL Device (III-2)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (III-P-2) obtained in Example III-6 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order LiF(film thickness 0.5 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the LiF/Al was the negativeelectrode, at about 5 V emission of orange light (λ=588 nm) wasobserved. No change in the color of this orange light emission wasobserved after 500 hours at 25° C.

Example III-10 Fabrication of Organic EL Device (III-3)

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example III-8 except that the metal coordinationcompound-containing copolymer (III-P-3) was used instead of the metalcoordination compound-containing copolymer (III-P-1). With regard to thecharacteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=460 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

Comparative Example 4

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example III-8 except that polydioctylfluorene was usedinstead of the metal coordination compound-containing copolymer(III-P-1). The ITO/light-emitting polymer layer/Ca/Al device thusobtained was connected to a power supply, a voltage was applied so thatthe ITO was the positive electrode and the Ca/Al was the negativeelectrode, and at about 6 V emission of blue light (λ=430 nm) wasobserved, but the color of the light emission changed from blue toyellowish green over time.

Example IV-4 Synthesis of Dicyclohexyloxybenzene Diboronic Acid Ester(IV-PP-1)

A Grignard reagent was prepared by gradually adding a THF solution of2,5-dibromo-1,4-dihexyloxybenzene (30 mmol) to a mixture of magnesium(1.9 g, 80 mmol) and THF under a flow of argon while stirring well. TheGrignard reagent thus obtained was gradually added dropwise over 2 hoursto a THF solution of trimethyl borate (300 mmol) at −78° C. whilestirring well, and the mixture was then stirred at room temperature for2 days. The reaction mixture was poured into 5% dilute sulfuric acidcontaining crushed ice and stirred. The aqueous solution thus obtainedwas extracted with toluene, and the extract was concentrated to give acolorless solid. The solid thus obtained was recrystallized fromtoluenelacetone (1/2) to give dicyclohexyloxybenzene diboronic acid ascolorless crystals (50%). The dicyclohexyloxybenzene diboronic acid (12mmol) thus obtained and 1,2-ethanediol (30 mmol) were refluxed intoluene for 10 hours, and then recrystallized from toluene/acetone (1/4)to give a dicyclohexyloxybenzene diboronic acid ester as colorlesscrystals (80%).

Example IV-5 Synthesis of Metal Coordination Compound-ContainingCopolymer (IV-P-1)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (1) synthesized in Example 1 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (8 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example IV-4(10 mmol), a tribromo branched monomer (1 mmol), represented by thestructural formulae below, and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow ofargon, and the mixture was refluxed for 48 hours while stirringvigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(IV-P-1).

Example IV-6 Synthesis of Metal Coordination Compound-ContainingCopolymer (IV-P-2)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (125) synthesized in Example 2 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (3.5 mmol),2-(2,5-dibromophenyl)-5-phenyl[1,3,4]oxadiazole (4 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example IV-4(10 mmol), a tribromo branched monomer (0.5 mmol), represented by thestructural formulae below, and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow ofargon, and the mixture was refluxed for 48 hours while stirringvigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

2-(2,5-Dibromo-phenyl)-5-phenyl-[1,3,4]oxadiazole

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(IV-P-2).

Example IV-7 Synthesis of Metal Coordination Compound-Containingcopolymer (IV-P-3)

A 2M aqueous solution of K₂CO₃ was added to a toluene solution of themetal coordination compound (253) synthesized in Example 3 (1 mmol),2,5-bis(4-bromophenyl)[1,3,4]oxadiazole (8 mmol),9,9-dioctylfluorene-2,7-diboronic acid ester (5 mmol), thedicyclohexyloxybenzene diboronic acid ester synthesized in Example IV-4(5 mmol), a tribromo branched monomer (1 mmol), represented by thestructural formulae below, and Pd(0)(PPh₃)₄ (0.2 mmol) under a flow ofargon, and the mixture was refluxed for 48 hours while stirringvigorously.

2,5-Bis-(4-bromo-phenyl)-[1,3,4]oxadiazole

9,9-Dioctylfluorene-2,7-bis(pinacol boronate)

2-(4-[1,3,2]Dioxaborolan-2-yl-2,5-dicyclohexyloxy-phenyl)-[1,3,2]dioxaborolane

The reaction mixture was cooled to room temperature and then poured intoa large amount of methanol so as to precipitate a solid. The solid thusprecipitated was filtered by suction and washed with methanol to give asolid. The solid thus obtained by filtration was dissolved in toluene,and then poured into a large amount of acetone so as to precipitate asolid. The solid thus precipitated was filtered by suction, and washedwith acetone to give a solid. The above-mentioned re-precipitation withacetone was repeated a further two times. Subsequently, after the solidthus obtained was dissolved in toluene, a cation/anion exchange resin(ion exchange resin manufactured by Organo Corporation) was addedthereto, and the mixture was stirred for 1 hour and then filtered bysuction to recover a polymer solution. The above-mentioned treatmentwith the ion exchange resin was repeated a further two times. Thepolymer solution thus recovered was poured into a large amount ofmethanol so as to precipitate a solid. The solid thus obtained wasfurther extracted and washed with acetone in a Soxhlet extractor for 24hours to give a metal coordination compound-containing copolymer(IV-P-3).

Example IV-8 Fabrication of Organic EL Device (IV-1)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (IV-P-1) obtained in Example IV-5 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order Ca(film thickness 20 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=445 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

Example IV-9 Fabrication of Organic EL Device (IV-2)

A toluene solution (1.0 wt %) of the metal coordinationcompound-containing copolymer (IV-P-2) obtained in Example IV-6 wasapplied by spin coating to a glass substrate with a 2 mm wide ITO(indium tin oxide) patterning under an atmosphere of dry nitrogen togive a light-emitting polymer layer (film thickness 70 nm).Subsequently, it was dried by heating at 80° C./5 minutes on a hot plateunder an atmosphere of dry nitrogen. The glass substrate thus obtainedwas transferred to vacuum vapor deposition equipment, and electrodeswere formed on the above-mentioned light-emitting layer in the order LiF(film thickness 0.5 nm) and Al (film thickness 100 nm). With regard tothe characteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the LiF/Al was the negativeelectrode, at about 5 V emission of orange light (λ=580 nm) wasobserved. No change in the color of this orange light emission wasobserved after 500 hours at 25° C.

Example IV-10 Fabrication of Organic EL Device (IV-3)

An ITO/light-emitting polymer layer/Ca/Al device was fabricated in thesame manner as in Example IV-8 except that the metal coordinationcompound-containing copolymer (IV-P-3) was used instead of the metalcoordination compound-containing copolymer (IV-P-1). With regard to thecharacteristics of the organic EL device at room temperature,current/voltage characteristics were measured using a 4140B picoammetermanufactured by Hewlett-Packard and the luminance was measured using anSR-3 manufactured by Topcon Corporation. When a voltage was applied sothat the ITO was the positive electrode and the Ca/Al was the negativeelectrode, at about 4 V emission of blue light (λ=455 nm) was observed.No change in the color of this blue light emission was observed after500 hours at 25° C.

1. A metal coordination compound-containing copolymer comprising: ametal coordination compound monomer unit represented by any one ofFormulae (1) to (6),

(in the formulae, M is Ir, Rh, Ru, Os, Pd, or Pt, and n is 1 or 2; ringA is a cyclic compound containing a nitrogen atom bonded to M; X₁ to X₇and R are independently substituents selected from the group consistingof —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, —SiR⁶R⁷R⁸, and —NR⁹R¹⁰ (here, R¹ toR¹⁰ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, aC1 to C22 straight-chain, cyclic, or branched alkyl group or acorresponding halogen-substituted alkyl group in which a part or all ofthe hydrogen atoms are substituted by a halogen atom, a C6 to C30 arylgroup, a C2 to C30 heteroaryl group, or a C7 to C30 aralkyl group, or acorresponding halogen-substituted aryl group, halogen-substitutedheteroaryl group, or halogen-substituted aralkyl group, in which a partor all of the hydrogen atoms are substituted by a halogen atom, and R¹to R¹⁰ may be identical to or different from each other), X₁ to X₇ maybe identical to or different from each other, and ring A may have asubstituent that is the same as the groups defined by X₁ to X₇; ring Cis a compound that is bonded to M and that bonds to a linking group; andring C may have a substituent that is the same as the groups defined byX₁ to X₇); and at least one type of monomer unit selected from the groupconsisting of a substituted or unsubstituted quinoline monomer unit, asubstituted or unsubstituted arylene and/or heteroarylene monomer unit,a substituted or unsubstituted branched monomer unit, and a substitutedor unsubstituted conjugated monomer unit.
 2. The metal coordinationcompound-containing copolymer according to claim 1, wherein thecopolymer comprises a metal coordination compound monomer unitrepresented by any one of the Formulae (1) to (6), a substituted orunsubstituted quinoline monomer unit represented by Formulae (13-1),

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene; and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O— (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and a substituted or unsubstituted arylene and/orheteroarylene monomer unit, the monomer units each being bonded via alinking group represented by Formula (14),-(G)b-  (14) (in the formula, G is a divalent group selected from thegroup consisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—,—SiR₂—O—SiR₂—, and —SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl orheteroaryl group), and b is an integer of 0 or 1).
 3. The metalcoordination compound-containing copolymer according to claim 1, whereinthe copolymer comprises a metal coordination compound monomer unitrepresented by any one of the Formulae (1) to (6), a substituted orunsubstituted quinoline monomer unit represented by Formulae (13-1),

(in the formulae, a plurality of V are independently substituentsselected from the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵,and —SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of a quinoline residue, and each a isindependently an integer of 0 to 3; D is selected from the groupconsisting of a single bond and arylene; and E is a divalent linkinggroup selected from the group consisting of a single bond, —O—, —S—,—C(O)—, —S(O)—, —S(O₂)—, —W—, —(—O—W—)m-O- (m is an integer of 1 to 3),and -Q- [in the formulae, W is a divalent group selected from the groupconsisting of —Ra—, —Ar′—, —Ra—Ar′—, —Ra′—O—Ra′—, —Ra′—C(O)O—Ra′—,—Ra′—NHCO—Ra′—, —Ra—C(O)—Ra—, —Ar′—C(O)—Ar′—, -Het′-, —Ar′—S—Ar′—,—Ar′—S(O)—Ar′—, —Ar′—S(O₂)—Ar′—, and —Ar′-Q-Ar′—; Ra is alkylene, Ar′ isarylene, each Ra′ is independently a group selected from the groupconsisting of alkylene, arylene, and a mixed alkylene/arylene group,Het′ is heteroarylene, and Q is a divalent group containing a quaternarycarbon]), and a substituted or unsubstituted branched monomer unit, themonomer units each being bonded via a linking group represented byFormula (14),-(G)b-  (14) (in the formula, G is a divalent group selected from thegroup consisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—,—SiR₂—O—SiR₂—, and —SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl orheteroaryl group), and b is an integer of 0 or 1).
 4. The metalcoordination compound-containing copolymer according to claim 1, whereinthe copolymer comprises a metal coordination compound monomer unitrepresented by any one of the Formulae (1) to (6), and a substituted orunsubstituted conjugated monomer unit represented by Formula (13-2),

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R₁ and R₂ mayindependently be a hydrogen atom; n, m, and 1 are independently 0 or 1,and n, m, and l are not simultaneously 0), the monomer units each beingbonded via a linking group represented by Formula (14),-(G)b-  (14) (in the formula, G is a divalent group selected from thegroup consisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—,—SiR₂—O—SiR₂—, and —SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl orheteroaryl group), and b is an integer of 0 or 1).
 5. The metalcoordination compound-containing copolymer according to claim 1, whereinthe copolymer comprises a metal coordination compound monomer unitrepresented by any one of the Formulae (1) to (6), a substituted orunsubstituted conjugated monomer unit represented by Formula (13-2),

(in the formula, Ar₁ and Ar₂ are divalent arylene and/or heteroarylene;a plurality of V, and R₁ and R₂, are independently substituents selectedfrom the group consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and—SiR⁶R⁷R⁸ (here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, orbranched alkyl group, or a C2 to C30 aryl or heteroaryl group), may beidentical to or different from each other, and are bonded to asubstitutable position of an arylene or heteroarylene residue, and a andb are independently an integer of 0 or greater; R₁ and R₂ mayindependently be a hydrogen atom; n, m, and 1 are independently 0 or 1,and n, m, and l are not simultaneously 0), and a substituted orunsubstituted branched monomer unit, the monomer units each being bondedvia a linking group represented by Formula (14),-(G)b-  (14) (in the formula, G is a divalent group selected from thegroup consisting of —O—, —R—O—R—, —S—, —NR—, —CR₂—, —SiR₂—,—SiR₂—O—SiR₂—, and —SiR₂—O—SiR₂—O—SiR₂— (here, R is a C1 to C22straight-chain, cyclic, or branched alkyl group, or a C2 to C30 aryl orheteroaryl group), and b is an integer of 0 or 1).
 6. The metalcoordination compound-containing copolymer according to claim 1, whereinthe substituted or unsubstituted branched monomer unit is a branchedmonomer unit selected from the group consisting of Formulae (15):

(in the formulae, a plurality of Y are substituents selected from thegroup consisting of —R¹, —OR², —SR³, —OCOR⁴, —COOR⁵, and —SiR⁶R⁷R⁸(here, R¹ to R⁸ are a C1 to C22 straight-chain, cyclic, or branchedalkyl group, or a C2 to C30 aryl or heteroaryl group), may be identicalto or different from each other, and are bonded to a substitutableposition of a benzene ring having a branched skeleton, and p is aninteger of 0 to 4).
 7. The metal coordination compound-containingcopolymer according to claim 1, wherein in the Formulae (I) to (6) ringA is pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole,benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole,benzopyrazoletriazine, or isoquinoline, which may have a substituentthat is the same as the groups defined by X₁ to X₇.
 8. The metalcoordination compound-containing copolymer according to claim 1, whereinin the Formulae (1) to (6) at least one of X₁ to X₇ and the substituentof ring A defined as being the same as X₁ to X₇ is a fluorine atom or atrifluoromethyl group.
 9. The metal coordination compound-containingcopolymer according to claim 1, wherein in the Formulae Formulae (1) to(6) M is iridium.
 10. A polymer composition comprising the metalcoordination compound-containing copolymer according to claim 1 and aconjugated or non-conjugated polymer.
 11. An organic electroluminescentdevice fabricated using the metal coordination compound-containingcopolymer according to claim
 1. 12. An organic electroluminescent devicefabricated using the polymer composition according to claim 10.